On Demand available April 26 - June 30, 2021 systems. Cr-rich samples presented faceted columns with intercolumnar pores and cauliflower-like surface morphology. The growth of the h-Cr2N Hard Coatings and Vapor Deposition Technologies phase caused a decrease of the grain sizes, and their morphology changed Room On Demand - Session B1 to pyramidal or stacked pyramids at lower duty-cycles. The transformation of the h-Cr2N to CrN leads to highly dense columnar microstructures, while PVD Coatings and Technologies the residual stresses of the coating increased with the higher duty-cycle.

Keywords: HiPIMS, duty-cycle, CrxN, graded microstructure. B1-1 On Electron Heating and Ion Recycling in the High Power Impulse Magnetron Sputtering Discharge, Jon Tomas Gudmundsson ([email protected]), B1-3 New Approaches for AlCrN-Based Coatings for High Speed University of Iceland; D. Lundin, Linköping University, Sweden; M. Raadu, Applications, Markus Schenkel ([email protected]), KTH Royal Institute of Technology, Sweden; T. Petty, T. Minea, LPGP, voestalpine Eifeler Vacotec GmbH, Düsseldorf, Germany; S. Spor, Universite Paris-Sud, France; N. Brenning, KTH Royal Institute of voestalpine Eifeler Vacotec GmbH, Düsseldorf, Germany, Austria; N. Technology, Sweden Gerhards, U. Zimmermann, F. Nahif, voestalpine Eifeler Vacotec GmbH, In the past it has been assumed that the magnetron sputtering discharge is Düsseldorf, Germany maintained by the sheath acceleration of secondary electrons emitted from The CO2 debate—a global challenge requires the necessity of renewed the target, upon ion impact. This is described by the well-known Thornton investments and innovations by manufacturers and suppliers with a strong equation, which in its original form [1] is formulated to give the minimum focus on an increase of sustainability. Especially, the automotive sector required voltage to sustain the discharge. However it has been (driven by the governmentally regulated CO2 emission limit), in detail the demonstrated recently that Ohmic heating of electrons outside the trends for the e-mobility, which has reached higher levels of importance. cathode sheath is roughly of the same order as heating due to acceleration Consequently, high-performance materials and versatile material across the sheath in dc magnetron sputtering (dcMS) discharges [2]. combinations with focus on weight reduction and energy-efficient Furthermore, for the high power impulse magnetron sputtering (HiPIMS) automotive design are replacing conventional materials. The trend to a discharge we find that direct Ohmic heating of the plasma electrons is reduction of the cycle times of the production lines, leads to new found to dominate over sheath acceleration by typically an order of challenges in the application of tools, such as higher mechanical and magnitude [3]. In HiPIMS discharge a high density plasma is created by thermal loads exposure during operation. applying high power pulses at low frequency and low duty cycle to a Thus, the talk will focus on the technical possibilities to overcome these magnetron sputtering device. Here we discuss the large discharge currents challenges by the appropriate choice of coating design using the example and the discharge current composition at the target surface in HiPIMS of aluminum-chromium nitride based coatings. discharges. We discuss the role of self-sputter(SS-) recycling and working gas recycling within the discharge. We find that above a critical current B1-4 Investigation of the Influence of the Thickness of Nanolayers in 2 density Jcrit ≈ 0.2 A/cm , a combination of self-sputter recycling and working Wear-resistant Layers of Ti-TiN-(Ti,Cr,Al)N Coating on Destruction in the gas-recycling is the general case [4]. For high self-sputtering yields, the Cutting and Wear of Carbide Cutting Tools, Alexey Vereschaka discharges become dominated by SS-recycling, contain only a few energetic ([email protected]), S. Grigoriev, MSTU Stankin, Russian Federation; N. secondary electrons. For low self-sputtering yields, the discharges operated Sitnikov, National Research Nuclear University MEPhI, Russian Federation; above Jcrit are dominated by working gas recycling, and secondary electrons J. Bublikov, Ikti Ran, Russian Federation play a more important role. We explore a discharge with Al target which The paper presents the results of the investigation into the formation of develops almost pure self-sputter recycling, a discharge with Ti target that the nanolayer structure of the Ti-TiN-(Ti,Cr,Al)N coating and its influence on exhibits a mix of self-sputter recycling and working gas-recycling [5] and a the thickness of coatings, their resistance to fracture in scratch testing, and reactive Ar/O2 gas mixture where working gas-recycling is dominating [6]. the wear resistance of coated tools in turning 1045 steel. The structure of [1] J A Thornton, J. Vac. Sci. Technol. 15 (1978) 171 the coatings with the nanolayer thicknesses of 302, 160, 70, 53, 38, 24, 16, [2] N. Brenning et al., Plasma Sources Sci. Technol. 25 (2016) 065024 and 10 nm was studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution (HR) TEM. It is [3] C Huo et al., Plasma Sources Sci. Technol. 22 (2013) 045005 shown that the grain sizes in the nanolayers decrease to certain values with [4] N. Brenning et al. Plasma Sources Sci. Technol. 26 125003 (2017) an increase in the thickness of the nanolayers, and then, with a further [5] C. Huo et al., J. Phys. D: Appl. Phys. 50 354003 (2017). decrease in the nanolayer thickness, the grain sizes of the nanolayer grow as the interlayer interfaces cease to produce a restraining effect on the [6] J. T. Gudmundsson et al. Plasma Sources Sci. Technol. 25, 065004 growth of the grains. The study found that the nanolayer thickness (2016). influenced the wear of carbide cutting tools and the pattern of fracture for

B1-2 Tailoring the Chemical Composition and Microstructure of CrxN the Ti-TiN-(Ti,Cr,Al)N coatings. Deposited by HiPIMS through Duty-cycle Modifications, Martha Cedeño- B1-5 INVITED TALK: Industrial Scale ta-C Coating Using Laser Arc Vente ([email protected]), G. Mondragón-Rodríguez, N. Technology, Wolfgang Fukarek ([email protected]), B. Camacho, A. Gómez-Ovalle, J. González-Carmona, J. Alvarado-Orozco, D. Gebhardt, VTD Vakuumtechnik Dresden GmbH, Germany; V. Weihnacht, F. Espinosa-Arbeláez , Centro de Ingeniería y Desarrollo Industrial (CIDESI), Kaulfuss, Fraunhofer IWS, Germany INVITED Mexico First reports about a Laser-initiated vacuum arc date back to 1976 /1/. The main challenge in hard coating manufacturing is developing dense, Laser ignition has many advantages particularly for pulsed high current flawless, and smooth surface morphology coatings, which improve the vacuum arcs when spatial and temporal control at high pulse repetition performance of components exposed to severe service conditions. One of rates for millions of pulses is required. This holds especially for the carbon the most promising coating techniques to achieve this goal is the High- arc which deviates markedly from metal arcs with respect to arc Power Impulse Magnetron Sputtering (HiPIMS), which produces highly movement, charge state and degree of ionization and particle generation. ionized plasmas, resulting in definite improvements on the film The carbon arc is preferentially operated at pulsed arc currents in the kA microstructure and properties. The application of pulses (50 - 500 μs) range and pulse lengths of some 100 µs. The Carbon Laser-Arc has been during the deposition process attains a high ionization rate in HiPIMS. The investigated and applied to deposition of highly tetrahedral amorphous pulse modification (e.g., duty-cycle, also known as τ) affects the current carbon films (ta-C) since the 1990th/2/. Only in recent years the Carbon density, modifying the stoichiometry and chemical composition of the Laser-Arc was introduced in mass production for coating of automotive coating; this indicates that the pulse appropriate selection is a viable and powertrain components as well as for other tribological applications and practical alternative for obtaining graded or multilayer metal nitrides at a cutting tools. In this paper we discuss different aspects of upscaling ta-C fixed gas flow, thus tailoring the coating internal stress distribution, Laser-Arc coating systems in order to increase the throughput and the total microstructure, and mechanical properties. amount of deposited carbon per batch. The importance of process stability In this work, the duty-cycle design to modify the chemistry, microstructure, for long coating runs is discussed. We also report on deviating film and residual stresses of CrxN coatings is presented and discussed. The properties that have been observed on films deposited at intermittent average current tends to increase from 2.9 to 12 % with the variation of τ high-rate deposition of ta-C. during the HiPIMS process. These process conditions lead to a significant /1/ J.E. Hirshfield, Laser-initiated vacuum arc for heavy ion sources. IEEE increment of the deposition rate and the chromium content in the CrxN Transact. Nucl. Sci. 23, 1006-1007 (1976) coating. Various crystalline phases like α-Cr, α-Cr + h-Cr2N, h-Cr2N, and h- Cr2N + c-CrN were obtained in the film, resulting in graded multilayer On Demand available April 26 - June 30, 2021 1 On Demand available April 26 - June 30, 2021 /2/ H.-J. Scheibe et al, Laser-arc: a new method for preparation of CapEx and operations costs, regulatory acceptance and quality assurance diamond-like carbon films. Surf. Coat. Technol. 47, 455-464 (1991). protocols, and applicability for both pressurized-water and boiling-water conditions. In this study we evaluate a high-throughput fabrication method B1-7 Key Importance of the Controlled Reactive HiPIMS for Low- for nanolayered Cr-based corrosion-resistant and fracture-resistant temperature Preparation of Tunable Oxynitrides and Thermochromic coatings using a high-power impulse magnetron sputtering innovation— Oxides, Jaroslav Vlček ([email protected]), J. Houška, University of West namely the IMPULSE® + Positive KickTM. Ultra-fast IMPULSE® switching Bohemia, Czech Republic achieves high instantaneous plasma densities during HIPIMS discharge Reactive high-power impulse magnetron sputtering (HiPIMS) with a pulse for easy control over self-sputtering, ionization fraction and reactive feedback pulsed reactive gas (oxygen and nitrogen) flow control and to- gas management. The adjustable Positive KickTM quickly reverses the substrate reactive gas injection into a high-density plasma in front of the polarity on the sputter target to accelerate metal ions to the substrate— sputtered metal target was used for a low-temperature deposition of increasing delivered ion fraction and rate for higher efficiency. Precision ion highly optically transparent Al-O-N films (substrate temperature of 120 °C) energy control results in fully dense films across a wider range of the and thermochromic VO2-based films (substrate temperature of 330 °C) Thornton diagram controlling film stress and morphology. Metals and onto unbiased substrates. ceramics are precision deposited with excellent adhesion, graded A modified version of HiPIMS, called Deep Oscillation Magnetron composite nanostructure and conformal layering for radiation hardness, Sputtering, was used to produce high-quality Al-O-N films with a gradually thermal shock- and oxidation-resistance. ~10µm Cr-based coatings were TM changed elemental composition (from Al2O3 in AlN), structure and deposited via IMPULSE® + Positive Kick on 9.5-mm diameter Zr-alloy properties. We give the basic principles of this controlled deposition, cladding with Ar and N2 gas pressure (0.5-5Pa), cathode power density (0.1- 2 TM maximizing the degree of dissociation of both O2 and N2 molecules in a 2kW/cm ), main pulse width (5-100µs), Positive Kick voltage (+0-600V), discharge plasma, which leads to a replacement of very different kick delay & width (0-100µs), and repetition rates up to 10kHz. Utility of in- TM reactivities of the O2 and N2 molecules with metal atoms on the surface of situ surface cleaning via the Positive Kick is also demonstrated for growing films by similar (high) reactivities of atomic O and N. adhesion. Samples were characterized pre- and post-testing using We developed a low-temperature scalable deposition technique for high- mechanical testing, optical and scanning electron microscopy (EDS, EBSD) and x-ray diffraction. Thin-film microstructure was evaluated using SEM, performance durable thermochromic ZrO2/V0.982W0.018O2/ZrO2 coatings. The EDS, EBSD and FIB. Corrosion tests were performed in an autoclave using V0.982W0.018O2 layers were deposited by controlled HiPIMS of V target, combined with a simultaneous pulsed DC magnetron sputtering of W boronated and lithiated water at 360°C at 18.7MPa over sequential time periods for weight gain and spallation/delamination inspection. target (doping of VO2 by W to reduce the transition temperature to 20-21 °C), in an argon-oxygen gas mixture. The effective pulsed oxygen flow Manufacturability estimates for volume Zr-alloy coating using a patent- control of the reactive HiPIMS deposition makes it possible to utilize the pending inverted cylindrical magnetron configuration optimized for conformal HiPIMS deposition is presented. enhanced energies of the ions bombarding the growing V0.982W0.018O2 layers for the support of the crystallization of the thermochromic phase in them B1-12 Multifunctional Coatings with Antifouling Properties, Jose Castro at the low substrate surface temperature of 330 °C and without any ([email protected]), I. Carvalho, M. Henriques, S. Carvalho, substrate bias voltage. We present the basic principles of this controlled University of Minho, Portugal deposition. Additive manufacturing (AM) is a hot topic nowadays, having a first order in B1-8 Monitoring Tantalum Nitride Thin Films Structure by Reactive importance in research trends, improving existent technologies and HiPIMS Magnetron Sputtering: From Microstructure to Properties, carrying them further. AM can be applied to all family types materials: Angeline Poulon-Quintin ([email protected]), A. Achille, metals, polymers, ceramics and compounds. Among abovementioned, ICMCB-CNRS, France; D. Michau, Univ. Bordeaux, ICMCB, France; M. ceramics have a huge importance and application in our current Cavarroc, Safran Tech, France technologies. Their capability to maintain functional properties for long Tantalum nitride thin films were deposited onto steel substrates using time periods combined with the easiness to process and abundance of raw Reactive High-Power Impulse Magnetron Sputtering (HiPIMS) allowing materials make them a fundamental part of mankind development. Within reaching a high ionization degree of the sputtered metallic material thanks this type of materials, one of the most commonly used nowadays is to high power density applied to the target during few tens of stoneware. This material has a wide range of uses, from everyday usage such as kitchenware and pottery to high tech applications such as pipelines, microseconds pulse. The influence of target power density, N2 partial which in some cases are affected by biofouling. Some ceramics are not able pressure, total gas (Ar + N2) pressure and target-to-substrate distance on film crystalline structure is reported. The structures obtained were to prevent the formation of biofouling formation which can affect their investigated by X-ray diffraction and transmission electron microscopy. finish and appearance. Trying to solve this issue, TiN and Ag:TiN with Cubic metastable phase or hexagonal stable phase can be successfully oxygen addition coatings in 3D printed stoneware, were presented as isolated in single phase continuous layer. The TaN crystalline phase multifunctional solution, in order to extend the performance of base obtained depends strongly on processing parameters especially pulse material, offering a variety in an aesthetical point of view and adding parameters. It is well known that TaN hexagonal single-phase continuous antibacterial properties. This study performed the aforementioned films by layer is difficult to isolate using conventional reactive magnetron reactive direct current (DC) magnetron sputtering. Films obtained were sputtering. Our previous study, based on RF magnetron sputtering, has characterized physical, chemical and morphologically, as well as their color shown TaN hexagonal structure formation to be enhanced in growth variation, roughness, wettability, antibacterial and antibiofouling conditions promoting adatoms mobility on the substrate surface. With resistance. The results revealed that the Ag doped coatings (with or HiPIMS, TaN hexagonal phase layer is much more difficult to obtain due to without oxygen addition) had an enhanced multifunctionality compared the increase number of process parameters to select, the specific with control samples (without Ag). The Ag nanoparticles addition created a composition and the energy of the plasma created. Comparison of surface with antibacterial and antibiofouling, in order to resist outdoors mechanisms involved during the stabilization of each TaN structure and aqueous environments, making these films able to be applied in depending on the process is presented as well as characterization of architectural pieces as sculptures or other decorative parts, maintaining microstructure, and properties (mechanical, electrical and optical). their properties with good aesthetical properties. B1-9 INVITED TALK: Multilayer nano-composite Oxidation-resistant B1-13 How to Deposit a Porous Thin Film by Magnetron Sputtering ?, Coatings for Accident-tolerant Nuclear Fuel Cladding using Reactive Diederik Depla ([email protected]), R. De Doncker, Ghent HiPIMS with Positive Kick and Precision Ion Energy Control, Brian Jurczyk University, Belgium ([email protected]), R. Stubbers, I. Shchelkanov, T. Without additional efforts, thin films deposited by magnetron sputtering Houlahan, Starfire Industries LLC, USA INVITED are dense due to the bombardment by sputtered atoms and reflected In the wake of the Fukushima nuclear accident in Japan there is worldwide neutrals. To overcome this intrinsic feature of magnetron sputtering, pressure to improve the accident tolerance of fuels used in light water several routes have been explored to deposit a porous thin film, and still to reactors. A near-term pathway is to deposit a thin protective coating benefit from the advantages of magnetron sputtering. directly on existing Zr-alloy fuel cladding trading coating properties (i.e. Increasing the deposition pressure and/or tilting the substrate belongs to chemical resistance, wear resistance, fracture toughness, radiation the most common approaches, but these strategies are plagued by damage), impact on neutron economy and thermal hydraulics, technical issues such as enhanced arcing, a low deposition rate, and limited manufacturing feasibility and implementation readiness, per cladding unit, scalability.

On Demand available April 26 - June 30, 2021 2 On Demand available April 26 - June 30, 2021 Another strategy is based on the deposition of a mixture of materials, or an intermixing predominantly occurs in liquid state while the mechanisms alloy which is chemically and/or physically treated to remove one of the based on solid-state diffusion play an insignificant role due to the sharp constituents. Dealloying by applying a heat treatment and subsequently temperature gradient (shallow heat-affected zone) below craters and very electrochemical etching is one example that belongs to this group of high cooling rates [1]. As a next step, the microstructure and phase methods. High temperature and/or (electro)chemical treatments limit the composition of the modified layers of Al-Cr composite cathodes with substrate choice, and are often environmentally harmful. varying grain sizes were studied. The results from high-resolution analysis This paper suggests an alternative approach based on the sputter techniques revealed that metastable phases, including quasicrystalline deposition of a powder mixture of a metal with NaCl [1]. The deposited phases, are formed during the solidification of arc craters and, hence, are layer is simply treated with water to dissolve the deposited salt, leaving a the constituting phases of the modified layers. The average cooling rate in 6 porous metal layer on the substrate. The thin films are deposited from a these rapid solidification processes was estimated to be in the order of 10 powder target composed of NaCl and metal powder. Due to the low K/s. Accordingly, to optimize the plasma properties for film and coating thermal conductivity of the target, the target gets hot. As a result, the salt depositions it is necessary to consider non-equilibrium phases of the alloy is sublimed while the metal is sputtered from the target. The film system as they might be present on the modified surface. This means that composition, and therefore the porosity, is controlled by the applied target the target’s or cathode’s microstructure and constituent phases need to be power. designed to enable the formation of phases with optimized cohesive energy during the rapid solidification of arc craters. This one-source approach without the use of film annealing or aggressive chemicals overcomes the major obstacles of other synthesis routes without compromising the benefits of magnetron sputtering. 1. Golizadeh, M., et al., J. Appl. Phys., 2020. 127(11). [1] Sputter deposition of porous thin films from metal/NaCl powder targets, R. Dedoncker, H. Ryckaert, D. Depla, Appl. Phys. Lett. 115(2019) B1-16 INVITED TALK: Coating Design and Mechanical Properties of 041601doi:10.1016/10.1063/1.51128225 Multicomponrnt AlTi(X)N Hard Coatings, Yin-Yu Chang B1-14 Evolution of the Microstructure of Sputter Deposited TaAlON Thin ([email protected]), National Formosa University, Taiwan INVITED Films with Increasing Oxygen Partial Pressure, Nina Schalk Due to economical demands to further increase the efficiency of ([email protected]), C. Saringer, Montanuniversitat Leoben, production processes, it is essential to exploit the full potential of wear Austria; A. Fian, Joanneum Research Forschungsgesellschaft mbH, Austria; resistant hard coatings. TiN and AlTiN-based coatings are widely used as V. Terziyska, M. Tkadletz, Montanuniversitat Leoben, Austria protective material for cutting tools, molds, and mechanical components in Recently, quaternary oxynitrides of transition metals and aluminum have mechanical industries. Low chemical reactivity of these hard coatings with attracted increasing interest due to their tunable properties. Within the workpiece materials protects against sticking and thus reduces the present work, a series of TaAl(O)N films was sputter deposited using adhesive wear. The most widespread wear resistant coatings are those constant nitrogen and varying oxygen partial pressures. The films were with the following chemical formula Ti-X-(N,C and B) (X = Al, Cr, C, Si, and B grown from single element Ta and Al targets. The deposition parameters etc.) which have proven to have excellent properties for industrial were adjusted to obtain a Ta/Al atomic ratio of ~50/50 for the oxygen-free applications in the cutting, forming and stamping fields. film and were held constant for the following depositions, with the In this study, the coating design, mechanical property, high temperature exception of the increasing oxygen partial pressure and compensatory oxidation behavior and cutting performance of multicomponent and decreasing argon partial pressure. Elastic recoil detection analysis revealed multilayered AlTi(X)N coatings, which X= Cr, Si and B etc., will be discussed. oxygen contents of up to ~26 at.%, while the nitrogen content decreased These high performance coatings can be deposited by using cathodic-arc from ~47 at.% in the oxygen-free film to ~35 at.% in the film with the deposition with arc cathodes or unbalanced magnetron sputtering. Various highest oxygen content, resulting in a significant decrease of the cathode targets, such as Ti, Cr, TiAl, TiAlSi, CrAlSi, and AlSi, are used for the metal/non-metal ratio with increasing oxygen partial pressure. The micro- deposition. The microstructure of the as-deposited and high temperature and bonding structures of the films were investigated by X-ray diffraction, annealed coatings was characterized by field emission scanning electron X-ray photoelectron spectroscopy, Raman spectroscopy and transmission microscope (FESEM), high resolution transmission electron microscope electron microscopy. All films exhibited a dominating face centered cubic (HRTEM) and X-ray diffraction (XRD) using Bragg-Brentano and glancing TaN-based structure with indications for an additional nanocrystalline angle parallel beam geometries. The mechanical properties including phase fraction, which increases with increasing oxygen partial pressure. In hardness and elastic modulus of the coatings were analyzed by a addition, the mechanical properties were evaluated by nanoindentation, nanoindenter with Berkovich indenter tip. yielding a decreasing hardness and elastic modulus with increasing oxygen Depending on the coating design, the deposited AlTi(X)N coatings showed content. B1-NaCl crystal structure and have multiple orientations of (111), (200), B1-15 Towards Knowledge-based Design of Multi-element Target and (220). The nanohardness, which measured by nanoindentation, of Materials, Mehran Golizadeh ([email protected]), these coatings possessed hardness higher than 30 GPa, depending on the Montanuniversität Leoben, Austria; A. Anders, Leibniz Institute of Surface gradient and multilayered structures. The high temperature oxidation test Engineering (IOM), and Felix Bloch Institute, Leipzig University, Germany; C. showed the oxidation rate during annealing depends on film composition Mitterer, R. Franz, Montanuniversität Leoben, Austria and microstructure. The oxide layer formed on the AlTiSiN coatings consists The increasing demand for multi-element thin films and coatings for of large TiO2 and AlTiSiN grains at the oxide-coating interface, followed by a layer of protective Al2O3 in the near-surface region. Interestingly, after multifunctional purposes has pushed the target and cathode material industry to produce multi-element products. Nowadays, alloyed and oxidation, the AlTiBN coating contained an oxide layer composed of composite targets are commonly employed in various physical vapor nanocrystalline Al2O3 and TiO2. No crystallite growth or phase transformation occurred in the unoxidized AlTiBN coating part after deposition technologies including magnetron sputtering and cathodic arc deposition. The targets, which serve as cathodes in the respective oxidation. The gradient, multilayered, and nanocomposite AlTi(X)N show significantly improvement of the lifespan of cutting tools and mechanical discharges, are exposed to the discharge plasma during the deposition process, which alters their surface properties such as phase and chemical parts. composition. The surface modifications are particularly severe for cathodic Keywords: Hard coating; Mechanical property; AlTiN; Multicomponent; arc deposition since the cathode spots impose countless melting- Multilayer solidification cycles on the target material near the surface, leading to the formation of a network of craters and a several 10 µm thick modified layer. The formation mechanisms and properties of the modified layer, semi- empirically quantified by the cohesive energy of the constituent phases, influence the charge states and kinetic energies of the ions and, hence, the film growth conditions and coating properties. In a first step, a Mo/Al multilayer cathode was designed to reveal information about the heat-affected zone below the craters as well as the evolution of material intermixing as the sequential cathode spot events take place. The modified layer is formed by micro-sized displacements of the cathode material during crater formation. In addition, the material On Demand available April 26 - June 30, 2021 3 On Demand available April 26 - June 30, 2021 Hard Coatings and Vapor Deposition Technologies advantages of the ALD technique to provide objects with enhanced Room On Demand - Session B2 functionalities or new products. To illustrate the opportunities and challenges of depositing conformal layers on either complex-shape or CVD Coatings and Technologies temperature sensitive objects or both, the talk will focus on ALD coatings on additive manufactured metallic structures and on biopolymers like B2-1 In-situ Investigation of the Oxidation Behaviour of Chemical Vapour cellulose matrices. The talk will include a discussion on their potential Deposited Zr(C,N) Hard Coatings Using Synchrotron X-ray Diffraction, applications in energy and packaging industry. Our recent results on Florian Frank ([email protected]), M. Tkadletz, C. Saringer, enhanced functionalities provided by ALD like surface finishing (color, Montanuniversität Leoben, Austria; A. Stark, N. Schell, Helmholtz-Zentrum surface smoothing), high temperature oxidation resistance and gas Geesthacht, Germany; C. Czettl, CERATIZIT Austria GmbH, Austria; N. diffusion barrier among others will be presented. The understanding and Schalk, Montanuniversität Leoben, Austria improvement of the chemical/thermal compatibility between the object to ZrN, ZrC and ZrC0.4N0.6 coatings were successfully deposited via chemical be coated and the coating will be discussed based on a comprehensive vapour deposition (CVD) in an industrial scale CVD plant on cemented evaluation of the structure and composition. carbide substrates and steel foils. The microstructure and the mechanical properties of the as-deposited coatings were investigated by scanning B2-6 INVITED TALK: Plasma-assisted Deposition using Microdroplets, electron microscopy, X-ray diffraction (XRD) and nanoindentation tests. To Tsuyohito Ito ([email protected]), K. Nitta, K. Terashima, The gain insight into the high temperature oxidation behaviour, in-situ University of Tokyo, Japan INVITED synchrotron XRD experiments were performed. Powdered samples were With recent development of atmospheric-pressure technologies, various annealed in air between 100 °C and 1000 °C, while 2D XRD patterns were plasma applications with liquid have been extensively studied. In this recorded. Subsequently, the 2D XRD patterns were azimuthally integrated presentations, we are demonstrating spherical particle deposition as well and the resulting 1D diffractograms were evaluated by sequential and as pattern drawing via atmospheric-pressure non-equilibrium plasma using parametric Rietveld refinement. Applying these techniques, the phase microdroplets. By using microdroplets, we can apply more various raw evolution during oxidation could be determined. The results were then materials hopefully obtaining certain controllability, which are difficult only correlated with differential scanning calorimetry measurements, in order with gas phase processing. to further illuminate the oxidation mechanism of each coating system. It The first part of the presentation will be demonstration of sub-micrometer was shown that all Zr(C,N) samples form tetragonal, cubic and monoclinic spherical particles deposition [1]. Here, we apply microdroplets as semi- ZrO2 phases, whereas the onset temperature of the individual phases closed micro-reactors to control size distribution of synthesized particles. A depends on the chemical composition. The investigated ZrCN coating mist atomizer was used to generate microdroplets with diameter of exhibits the highest oxidation resistance, followed by ZrC and ZrN. approximately 5 μm. Such microdroplets were carried by He gas to the B2-3 Ti-Si-B-C-N PECVD Nanocomposite Coatings for Tribological plasma reactor. Zinc acetate (Zn(Ac)2) solution was used as a raw material Applications at Elevated Temperatures, Alexander Nienhaus for ZnO particles synthesis and the concentration was regulated at 0.5, 1, ([email protected]), TU Braunschweig, and 2 mM (mol/L). The generated particles are deposited on a silicon Institute for Surface Technology, Germany substrate locating under the plasma generator. The size distributions of the generated particles agree well with the ones expected by the distribution With increased demands for service lifetime of tools in hot forming of microdroplets and the concentrations of the raw materials; applications, e.g. extrusion molding and die-casting, surface modifications demonstrating that one particle is generated from one microdroplet in of hot working steels play an important role to improve its tribological conditions tested here. Thus microdroplets could be used as semi-closed properties under thermal load conditions. The machining of aluminum (Al) micro-reactors at least for controlling particle sizes. and copper (Cu) is especially challenging, considering its tendency to stick at the tools surface, which is increasingly impactful at elevated The later part of the presentation will be about plasma-assisted inkjet temperatures. Developing Ti-Si-B-C-N PECVD nanocomposite coatings is a printing (PIP), where a microdroplet is injected through plasma by an inkjet promising approach, because, with an adequate Si-content, thermal system. By using an inkjet system, the controllability of a microdroplet in stability and oxidation resistance can be increased by forming a thin, time and space can be significantly improved, developing a new printing amorphous (a-) Si3N4 tissue layer between the nanocristalline (nc-) grains, technique, PIP. So far, we have successfully demonstrated silver line mostly nc-TiN, ncTiC, and nc-TiCN. In this study, the influence of nitrogen drawing [2] as well as the simultaneous polymerization of 3,4- on its thermal and mechanical properties is under investigation. The N- ethylenedioxythiophene (EDOT) monomer stock solution ink and printing content ranged from 0.0..14.6 at.-%. Chemically stable TiB2 phases are of the resulting poly(3,4-ethylenedioxythiophene) (PEDOT) [3]. With silver formed by adding BCl3 to the PECVD coating deposition process. These line fabrications, compared with heat treatment, the line with lower phases are not observed in XRD-diffraction patterns, which indicates a-TiB2 electrical resistivity and a narrower width could be achieved with a much rather than ncTiB2, e.g. in contrast to Ti-B-N nanocomposite coatings. With shorter treatment time. As for PEDOT line fabrications, it was C-contents up to 32 at.-%, formation of a-C particles in the a-matrix is demonstrated that plasma-assisted chemical reactions could be combined likely. High temperature (T = 750-900 °C) in-situ XRD-measurements in air with inkjet printing method. atmosphere provided by synchrotron radiation showed different behavior Details will be presented at the conference. in oxidation resistance, with dependence of N-content. Furthermore, [1] M. Tsumaki, Y. Shimizu, T. Ito, Materials Letters 166, 81 (2016) tempering in air atmosphere at 850 and 900 °C for 30 and 60 min was carried out to gain additional information on the oxidation resistance. In [2] M. Tsumaki, K. Nitta, S. Jeon, K. Terashima, T. Ito, J. Phys. D: Appl. Phys. contact with molten or close to molten Al or Cu, Bcontaining 51, 30LT01 (2018) nanocomposites are expected to reduce the adhesive wear on the tools [3] K. Nitta, M. Tsumaki, T. Kawano, K. Terashima, T. Ito, J. Phys. D: Appl. surfaces. The multiphase coatings form compositionally complex Phys. 52, 315202 (2019) nanostructures, leading to a universal hardness of up to 39 GPa, close to the so called ‘superhardness’ (> 40 GPa). The starting point of oxidation B2-8 High Throughput Deposition of Hydrogenated Amorphous Carbon was determined to be in the range of 850-900 °C, underlining the possible Films using High-Pressure Ar+CH4 Plasmas, Kazunori Koga application as protective coating for hot forming tools. Further work will ([email protected]), S. Hwang, K. Kamataki, N. Itagaki, M. Shiratani, focus on the nanocomposite structure, the mechanical properties, and pin- Kyushu University, Japan on-disc tests at T = 750 °C with Al2O3 counterparts. Plasma chemical vapor deposition (CVD) method has attracted much attention for fabricating hydrogenated amorphous carbon (a-C:H) films B2-4 INVITED TALK: Atomic Layer Deposition for Complex-Shape and because it can realize to deposit large area films with a good uniformity [1]. Temperature Sensitive Objects: Towards New Functions and Products, In the conventional plasma CVD, the working gas pressure was the range Frédéric Mercier ([email protected]), Univ. Grenoble between 0.05 Torr and 1 Torr. The lifetime of carbon-related radicals tends Alpes, CNRS, France INVITED to be shorter for larger gas pressure resulting in a low deposition rate. Here Atomic Layer Deposition (ALD) technique finds many applications today in we found a high rate deposition of a-C:H films with high-pressure Ar+CH4 the fields of microelectronic, batteries and catalysts. Indeed, the intrinsic plasmas. advantages of ALD like conformality, uniformity and precise control of the The experiments were carried out using a capacitively coupled plasma thickness at the atomic scale can meet the requirements of the increasing reactor [2, 3]. Ar diluted CH4 gas was introduced to the chamber. The total complexity and the variety of objects to be coated. Besides the gas flow rate and CH4 concentration were at 98.8 sccm and 3.8 %, aforementioned fields, other emerging fields can benefit from the respectively. A 1cm x 1cm Si substrate was placed on a substrate holder. 28 On Demand available April 26 - June 30, 2021 4 On Demand available April 26 - June 30, 2021 MHz voltage of 170 V was applied to the powered electrode. The substrate concepts with well-controlled deposition conditions to maintain the temperature was room one. To analyze the deposition rate and the mass deposited “thin film” at early stage, nucleation regime. As a consequence, density, a scanning electron microscopy (JEOL JIB-4600F) and microbalance the “thin film” would maintain at the island forms or (Mettler Toledo) were used. particles/nanoparticles states with the size smaller than 100 nm at least in We have examined dependence of substrate position from the powered one dimension, whilst the alumina matrix would keep depositing to form a electrode on deposition rate as a parameter of the gas pressure. For the continuous matrix. Ultimately, a nanocomposite coating can be formed pressure below 2 Torr, the deposition rate monotonically decreases with with improved wear resistance and metal-cutting performance. The ability increasing the distance d between the powered electrode and the to process nanocomposite by direct nucleation and growth of ceramic substrate from 20 nm/min to 10 nm/min. In contrast, for the pressure materials via CVD technique should provide new technical opportunity on above 5 Torr, the deposition rate decreases from around 60 nm/min for d= the advanced materials and application development. 15 mm to about 30 nm/min for d= 30 mm. Photos of the plasmas suggest Keywords: CVD, Al2O3-based nanocomposite, thin films, nucleation, crystal that the radical generation tends to be localized near the powered growth electrode and the rate increases with the gas pressure in the region. Therefore, the high deposition rate realizes for d= 15 mm for 5 and 7 Torr. B2-11 Compatibility of a CoCrFeNi Multi-principal Element Alloy Substrate The mass density for 7 Torr and d=15 mm is 1.41 g/cm3. To further improve with Halide-based Thermal CVD Processes for TiN Deposition, Katalin the film characteristics, we studied the effects of dc pulse bias on the Böör ([email protected]), Uppsala University, Sweden; R. Qiu, substrates. A dc pulse bias voltage Vdc with 1 μs in the pulse duration and Chalmers University of Technology, Sweden; A. Forslund, KTH Royal 25 kHz in the reputation frequency was applied to the substrates. We Institute of Technology, Sweden; O. Bäcke, Chalmers University of found high mass density film of 1.67 g/cm3 is deposited at 66.7 nm/min for Technology, Sweden; H. Larsson, KTH Royal Institute of Technology, Sweden; E. Lindahl, Sandvik Coromant R&D, Sweden; M. Halvarsson, Vdc= -202 V. This indicates that the impinging ions can modify the newly deposited films and generate the dangling bonds at the surface, leading to Chalmers University of Technology, Sweden; M. Boman, Uppsala the determination of the mass density and deposition rate [4]. University, Sweden; L. von Fieandt, Sandvik Coromant R&D, Sweden Multi-principal element alloys (MPEAs) are materials consisting of at least [1] K.J Clay et al, J. Diam. Relat. Mater, 7,1100 (1998). four metallic elements in near–equimolar amounts. These alloys can exhibit [2] X. Dong et al, J. Phys: Conf. Ser., 518, 012010 (2014). new combinations of material properties, either deriving from the new [3] K. Koga et al, Jpn. J. Appl. Phys, 55, 01AA11 (2016). phases formed or from the individual components. Their applications may require a protective coating, it is therefore crucial to investigate their [4] M. Shiratani et al, J. Surf. Coat. Technol, 228, 15 (2013). compatibility with conventional coating technologies. Titanum nitride is a B2-9 Influence of Co-enriched Surface Zones in WC-Co Cemented Carbides widely used corrosion- and wear resistant coating, which is frequently on the Microstructure and Mechanical Properties of TiC0.6N0.4/α-Al2O3 deposited by CVD. This presentation assesses the compatibility of the Coatings, Fabian Konstantiniuk ([email protected]), CoCrFeNi substrate, an important MPEA, with a conventional CVD process M. Tkadletz, Montanuniversität Leoben, Austria; C. Czettl, CERATIZIT for TiN deposition using TiCl4/H2/N2 as precursors [1]. Different reactions Austria GmbH, Austria; N. Schalk, Montanuniversität Leoben, Austria between the substrate, the coating and the precursors will be discussed. In metal cutting applications functionally graded near surface zones in WC- These include substrate etching by Cl-containing species and intermetallic Co cemented carbide substrates are applied to optimize their properties, in compound or nitride building between the substrate elements and Ti or N, particular toughness and hardness. Thus, the present work focuses on the respectively. Substrate etching can result in voids in the substrate and the influence of Co-enriched substrate surface zones and their thickness on the substrate elements may be redeposited and incorporated in the coating. microstructure and mechanical properties of state-of-the-art TiC0.6N0.4/α- Intermetallic compounds and nitrides can be formed by diffusion of the Al2O3 coatings synthesized using chemical vapor deposition. substrate elements into the coatings or Ti/N diffusion into the substrate. Complementary cross-sectional energy dispersive X-ray spectroscopy and SEM, XRD and (S)TEM combined with EDS were used to determine which of electron back-scatter diffraction maps provided insight into the grain size, the mentioned processes take place in the CoCrFeNi-TiCl4/H2/N2 system preferred orientation and phase composition of coatings and substrates. between 850-950 °C. Thermodynamic calculations were carried out using While the hardness and Young´s modulus of the coatings were hardly the Thermo-Calc software to determine the stable compounds that can be affected by the Co–enriched surface zone and its thickness, formed during the process. nanoindentation maps performed on the cross-sections of the substrates The substrate was stable under the process conditions. Only Cr was confirmed a lower hardness and Young´s modulus in zones with higher Co reactive towards the N2 precursor and appeared in the coating grain content. Since the tensile residual stress in both, the TiC0.6N0.4 and α-Al2O3 boundaries, shown by EDS in TEM. Thermodynamic calculations predicted decreased with increasing thickness of the Co–enriched surface zone, as that Cr-containing nitride phases could form, explaining the driving force determined by X-Ray diffraction, it is suggested that stress relaxation for Cr diffusion in the grain boundaries. XRD results only indicated the occurs through plastic deformation of the soft Co-enriched surface zone. presence of a TiN and a CoCrFeNi phase. No intermetallic phases were Despite the influence on the residual stress, the Co–enriched surface zone formed between the substrate elements and titanium and no signs of and its thickness was found to have no effect on the thermal crack etching were observed. networks of the coatings. However, Rockwell-indentation tests The results provide an understanding on the processes involved in the demonstrated a reduction of the coating adhesion with increasing substrate-precursor interaction and the driving forces behind. They explain thickness of the Co–enriched surface zone. The results obtained within this why CoCrFeNi outperforms elemental Ni, Fe [2] and alloys of its work contribute to a better understanding of the influence of a Co- components, giving a basis for determining which multi-component alloys enriched surface zone and its thickness on the performance of TiC0.6N0.4/α- can be compatible with conventional CVD processes. Al2O3 coated cutting tools. [1] Böőr, K. et al., Surf. Coatings Technol. 393, 125778 (2020) B2-10 CVD Alumina-based Nanocomposite Coatings, Zhenyu Liu [2] von Fieandt, L. et al., Surf. Coat. Technol.334, 373–383 (2017) ([email protected]), Kennametal Inc., USA Nanocomposite is a multiphase solid material where one of the phases has B2-12 Silicon Carbide Coatings for High Temperature Receiver of the size of less than 100 nanometers (nm) in at least one dimension, or Concentrated Solar Power Plants, Michel Pons (michel.pons@grenoble- structures having nano-scale repeat distances between the different inp.fr), D. Chen, University of Grenoble Alpes, France; J. Colas, PROMES- phases that make up the material. Nanocomposite coating represent a new CNRS, France; F. Mercier, University Grenoble-Alpes, France; L. Charpentier, generation of materials exhibiting completely new properties with respect M. Balat-Michelin, PROMES-CNRS, France to the conventional used materials. The superior mechanical properties of There is a growing interest in concentrating solar power plants as electricity nanocomposites originate from their peculiar nanostructures (size effects) generation systems. M irrors concentrate the sun's energy to drive and high density of interfaces. The unique structure and exceptional traditional steam turbines or engines that create electricity. The thermal properties make nanocomposite materials a possible alternative to energy concentrated in a CSP plant can be stored and used to produce traditional polycrystalline materials, which have met their limits in many electricity when it is needed, day or night. One of the challenges is to build recent engineering applications. the solar receiver which can work at temperatures near or higher than Inspired by nanolayer coatings of PVD and multilayer CVD coatings 1000 °C for optimizing the yield. Current candidate materials are metallic alloys such as Inconel, or bulk ceramics like silicon carbide, but their development, we demonstrate a couple of potential Al2O3-based nanosomposite systems deposited by CVD process directly using multilayer operating temperatures may be limited due to oxidation or mechanical On Demand available April 26 - June 30, 2021 5 On Demand available April 26 - June 30, 2021 problems. Silicon carbide coatings, deposited by chemical vapor deposition B2-15 Investigation of Diamond Coating Characteristics on Chrome-Plated technology at 1100 °C, are selected for their high thermal conductivity, low AISI 4140 Steel by Hot-Filament Chemical Vapour Deposition Process, R. thermal expansion coefficient, high temperature stability and oxidation Vignesh, S Boominatha Sellarajan ([email protected]), J. resistance. They forms stable and protective silica scales at temperatures Rajaguru, N. Arunachalam , M. Ramachandra Rao, Indian Institute of higher than 1000°C. Oxide dispersion strengthened (ODS) FeCrAl alloys Technology Madras , India (Kanthal APMT), are alumina-forming alloys which can resist to high In the modern engineering world, extensive research has led to the temperature oxidation. They are chosen as model substrates to study the development of certain unique grades of steel, mostly suitable for potential of SiC coatings. Accelerated cyclic oxidation and high temperature enhanced functions. AISI 4140 steel is one such grade, having major emissivity measurements are performed in Promes solar furnace facilities applications in power plants, automobile and aerospace industry. HFCVD (France), confirming the potential of silicon carbide coatings as materials process on these steel substrates have attracted significantly to improve for high temperature central receivers. The SiC based multilayered system the mechanical performances due to the superior properties of diamond exhibits low degradation after 1500 h of oxidation at 1000 °C in air. The films. However, CVD diamond films on steel are a great challenge due to modelling and simulation of stresses during thermal cycles taking into the formation of interfacial graphite layers; intrinsic stresses and high account the creep and growth of the oxide layer are used to show the stiffness due to considerable differences in thermal expansion coefficients limits of use of these materials. between substrate and diamond. This may lead to premature failure of diamond films. To overcome these limitations, interlayers such as Cr, Ti, B2-13 Hot Filament CVD Diamond Coatings for Hard-to-machine Mo, W, etc., were demonstrated for an improved adhesion by different Materials, Michael Woda ([email protected]), W. Puetz, M. techniques (sputtering and CVD). In this work, Cr interlayer made by hard- Frank, W. Koelker, C. Schiffers, O. Lemmer, CemeCon AG, Germany chrome plating technique was utilized. Then, diamond film was deposited In the group of carbon-based coatings, polycrystalline CVD diamond thin over Cr interlayer by HFCVD process. High substrate temperature (~750℃) films reveal some extraordinary material properties. Applying the very high generated during the diamond deposition can significantly affect the hardness of up to 10000HV onto cutting tools enables economically mechanical properties of the steel substrate as the material undergoes feasable tool usage when machining very high abrasive materials. CVD phase transformation. This leads to material failure in real-time diamond thin films are typically coated by either microwave or hot filament applications. Despite this, the necessary investigation about the influence CVD techniques. On cutting tools with cemented carbide substrates and of diamond coating deposition temperature on the microstructure and complex geometries hot filament CVD is well established on an industrial mechanical properties of the steel substrate has not been covered yet. scale nowadays. The basics of hot filament CVD diamond coating Hence, this work aims at analyzing the substrate properties at varying technology are briefly introduced in the scope of this presentation. The temperature (450-750℃) by adjusting the hot-filament to substrate films coated by this method can be utilized to address cutting of work piece distance (d: 20-40 mm) and the filament temperature (1800-2200℃) and materials including Carbon fiber reinforced plastics (CFRP), ceramics, deposition time (soaking time: 1-8 hrs). Tensile strength, ductility, XRD and graphite, Aluminum-Silicon alloys or even sintered carbide. This work microstructure via SEM were carried out. The results indicate that the presents results of case studies revealing the benefits of CVD diamond mechanical properties and microstructural features of the steel are coatings upon cutting operations on these very demanding work piece affected significantly by deposition temperature and time. The strength materials. and hardness of AISI 4140 steel drop as the deposition temperature and B2-14 Ald-Pvd Multilayers: Deposition, Thermal Stability And Mechanical time are increased. However, the ductility increased with increasing Properties, Thomas Edwards ([email protected]), T. Xie, L. deposition temperature and holding time. Microstructural observations Petho, S. Büchel, X. Maeder, B. Putz, J. Michler, Empa, Swiss Federal reveal that the carbide precipitates have a plate-like structure at lower Laboratories for Materials Science and Technology, Thun, Switzerland temperatures, but are spheroid-like at high temperatures. Carbide The extent of the embrittlement in ductile-brittle multilayers often formations at high temperature were also confirmed by the XRD analysis. These results suggest that it is essential to select an optimal depositing depends on the modulation period (tbrittle + tductile) as well as on the temperature and time by considering the material high-temperature modulation ratio (tbrittle/tductile) [1]. In this work, ductile-brittle multilayers of behaviour. Further, a case study on diamond film formation as a function of Al / Al2O3 / Al… and Ti / TiO2 / Ti… were produced on Si substrates by a filament-substrate gap is discussed. unique combination of atomic layer (ALD, Al2O3, TiO2) and physical vapor deposition (PVD, Al, Ti) within a single deposition system. Using this B2-16 The Challenge and Strategy of a-Si CVD Coating on Aluminum ALD/PVD combination, neighbouring layer thicknesses can easily differ by Alloys, Min Yuan ([email protected]), SilcoTek Corporation, USA one order of magnitude or more. In particular, the ability to deposit Aluminum alloys in general present a particular challenge in thermal CVD of continuous sub-nm layers with ALD opens up a wide range of otherwise amorphous silicon coating. unachievable modulation and thickness ratios. The thicknesses and structures of the ALD layers were verified by HR-TEM imaging of lift-outs. Aluminum is known to catalyze the crystallization of amorphous silicon and Further depositions on flexible substrates have also been performed with induce nanowire growth under thermal CVD conditions. The deposited thin film usually contains a mixture of amorphous and microcrystalline silicon, thinner Al layer thicknesses to minimize residual stresses. The Al2O3 or TiO2 layer thickness is varied across the multilayer cross-section (0.1 nm – 10 which not only manifest as undesirable cosmetic defects on finished nm) to study the effect on strength of the film as determined by products, but also compromise other coating properties such as coating microcompression, and on crack onset and propagation as a function of adhesion, corrosion resistance and chemical inertness. oxide layer thickness in tensile tested multilayer films. Single layered films Here we present a modified thermal CVD process that is designed to prime (Al or Al2O3, etc.) are used as reference materials. Further the thermal the aluminum substrate at the beginning of CVD, so that subsequent a-Si stability of such multilayer films was studied up to 0.9 T/Tm, considering the deposition can proceed smoothly. The priming step acts to prevent stability and crystallinity of the ALD interlayers and the texture of the PVD aluminum from catalyzing the amorphous-to-crystalline transition and stop layers. Grain growth of Al is limited by the Al2O3 layer, allowing for easy the undesirable silicon nanowire growth. The coated products from this discrimination of individual Al layers necessary for locating onset of cracks, process deliver more appealing cosmetic finish, as well as superior coating and for cross-sectional fragmentation analysis by focused ion beam (FIB) properties that will be discussed in the presentation. cross-sectioning under tension which avoids crack closure upon unloading. The priming effect is achieved by exposing the aluminum substrate to a The multilayer structure has good adhesion between individual layers as mixture gas at the initial stage of the CVD process. The synergistic reaction well as to the polymer substrate and the oxide layers show increasing of the gas mixture deposits a thin barrier layer at the substrate/coating stretchability with decreasing film thickness, as a result of being extremely interface, which serves to cut off the negative influence of aluminum on well defined and practically defect free. This study helps improve the the coating. The barrier layer itself has strong adhesion to both the understanding of deformation mechanisms in flexible thin film structures aluminum substrate and the a-Si coating deposited on top of it, thus and can give useful guidelines for strong and damage tolerant thin film improving the overall adhesion properties. metallic systems. This modification is easily incorporated as part of the CVD process and does [1] K. Wu, J.Y. Zhang, J. Li, Y.Q. Wang, G. Liu, J. Sun, Acta Mater. 100 (2015) not require separate wet chemistry or vacuum break. This makes it 344–358. straightforward to implement and scale up in a manufacturing setting, as has been demonstrated in the facility at SilcoTek Corporation.

On Demand available April 26 - June 30, 2021 6 On Demand available April 26 - June 30, 2021 Hard Coatings and Vapor Deposition Technologies outstanding properties and the possibility to up-scale the deposition Room On Demand - Session B3 process. These ta-C coatings are special representatives of the DLC coatings and unsurpassed in terms of their hardness and usability. Moreover, they Deposition Technologies and Applications for Diamond-like can be prepared almost free of intrinsic stress. Using optimal deposition Coatings parameters, a hardness of up to 70 GPa with Young's moduli of 700 to 800 GPa can be achieved, which leads to an extremely high operational wear B3-1 'Hydrogenated Amorphous Carbon from Magnetized Hollow resistance. Due to the low average surface roughness (Ra) of a few Cathode Discharges, John Miller ([email protected]), A. Ceballos- nanometers and the low friction coefficient these layers are also excellently Sanchexz, S. Elhadj, S. Kucheyev, B. Bayu Aji, S. Falabella, Lawrence suitable for tribological applications. By using optimized adhesion layers or Livermore National Laboratory, USA layer systems it is possible to achieve high adhesion strengths on a variety Diamond-like carbon is a popular hard coating material whose properties of substrate materials. The low temperature required during the deposition widely depend on deposition process and conditions within the process. process (< 90 °C) makes it also possible to coat temperature-sensitive Variations between the methods and conditions yield films with varying materials. Due to their chemical resistance, biocompatibility and dopability hydrogen, sp2 carbon, and sp3 carbon content who have densities the ta-C coatings offer a wide range of further applications, such as in between 1 and 3 g/cc, spanning the difference between a low-density medical technology, food industry or sensor technology. By means of the hydrocarbon polymer and polycrystalline diamond (high density carbon). combined pulsed laser deposition and laser pulse annealing process the This material is becoming increasingly interesting as a new ablator material LHM is able to produce homogeneous layers with a thickness ranging from for inertial confinement fusion because it is low Z and has the potential to a few nanometers up to a few 10 µm with an adjustable hardness between tune its density between that of glow discharge polymer(~1 g/cc) and 25 and 70 GPa and an adjustable intrinsic stress between 12 GPa and diamond (3.5 g/cc), two ICF ablator materials of choice. This work nearly zero GPa by choosing the corresponding deposition parameters. investigates the use of a magnetized hollow cathode discharge for That makes it also possible to prepare material and application specific depositing thick, density tunable amorphous carbon films for future inertial layer designs like Young's modulus gradients or multilayers. It will be confinement fusion experiments.A variety of the properties of the films will shown that the deposition process can be up-scaled to industrial be discussed including: composition, density, impurity content, thickness requirements using new high power excimer lasers, which were introduced limitation, deposition rate and surface morphology. in 2019. The LHM is now looking for interested partners and potential IM Release: LLNL-ABS-814679 customers. B3-2 Effect of Mechanical and Thermochemical Tool Steel Substrate Pre- B3-4 DLC Coatings Deposited by Novel Doping Strategies with HiPIMS, treatment on DLC Coating Durability, Daniel Tobola José Antonio Santiago Varela ([email protected]), I. ([email protected]), Łukasiewicz Research Network - Fernández-Martínez, A. Wennberg, Nano4Energy SL, Spain; M. Monclús, J. Krakow Institute of Technology, Poland; T. Liskiewicz, Manchester Molina-Aldareguia, IMDEA Materials Institute, Spain; V. Bellido-Gonzalez, Metropolitan University, UK; L. Yang, Leeds University, UK; T. Khan, Gencoa Ltd, UK; M. Panizo-Laiz, Universidad Politecnica de Madrid, Spain; Manchester Metropolitan University, UK; Ł. Boron, Łukasiewicz Research J. Sánchez-Lopez, T. Rojas, CSIC, Spain; S. Goel, Cranfield University, UK; J. Network - Krakow Institute of Technology, Poland Endrino, IKERBASQUE, Spain DLC coatings are becoming well established across many industrial sectors Diamond-like Carbon (DLC) coatings have been recognized as one of the including aerospace, automotive, oil and gas, and cold forming tools. While most valuable engineering materials for various industrial applications DLC coatings exhibit good mechanical properties and low coefficient of including manufacturing, transportation, biomedical and microelectronics. friction for themselves, DLC coating–substrate systems may suffer from Among its many properties, DLC stands out for a good frictional behaviour insufficient wear resistance. This paper describes the wear mechanisms combined with high surface hardness, offering an elevated protection and reports characteristics of the DLC coating-steel substrate system against abrasive wear. Nevertheless, a factor limiting the widespread behaviour after mechanical and thermochemical steel substrate pre- application of DLC coatings is their thermal stability. DLC is very 3 2 treatments. We have investigated two tool steel substrates, Sverker 21 temperature-sensitive since its sp -sp structure undergoes a graphitization (AISI D2) and advanced powder metallurgy alloyed steel Vanadis 8. Initially, process at high temperatures that deteriorates both hardness and the substrates were heat treated in vacuum furnace and gas quenched coefficient of friction. In order to overcome this limitation, new ways to resulting in hardness of 59±1 and 64±1 HRC respectively. Subsequently the modify DLC coatings for acceptable high temperature performance have samples were subjected to mechanical turning and burnishing with 130N been explored. In this work, we investigated a novel deposition technique and 160N forces, using diamond composite tools with ceramic bonding of hard DLC coatings doped with various elements (e.g. W, Cr, Ti, Si) using phase. Afterwards, a vacuum nitriding process in a PVD chamber as a pre- HiPIMS by incorporation of positive pulses. Highly ionized plasma treatment for subsequent DLC coating deposition was carried out. Coated discharges were obtained during HiPIMS deposition. The high ion energy 3 2 samples were subjected to a series of ball-on-disc wear tests against Al2O3 bombardment resulted in a higher sp to sp bond ratio. EELS and Raman 3 2 and Si3N4 counterparts. X-ray diffraction (XRD), instrumented indentation spectroscopy were used to characterize the sp and sp structures in the and scanning electron microscopy (SEM) were employed to examine the deposited films. Nanoindentation tests revealed improved mechanical phase composition, nano-hardness, Young’s modulus, surface properties (hardness up to 35 GPa) for doped DLC coatings. Additional high microstructure, elemental distribution and 3D surface topographies of the temperature nanoindentation tests performed in the range of 27 ºC to 450 wear scars. Selected variable factors including the type of steel, the ºC showed that the mechanical properties at high temperature are 3 burnishing force, type of counter-body material were subjected to dependent on the sp content. Pin-on-disk tests were carried out in order statistical analysis. The effect of sequential processes used as pre- to assess the tribological performance of the coatings both at room and treatment on DLC coating durability was demonstrated and the results are high temperature. The increased toughness and reduced compressive 3 discussed in light of improving the cold forming tools tribological stress that doping provides to the carbon matrix together with a high sp performance. bonding structure obtained with HiPIMS deposition improves the stability of DLC coatings for high temperature tribological applications. Finally, Keywords: DLC coatings, tool steels, vacuum nitriding, slide burnishing micromilling trials were carried out to assess the performance of these B3-3 Stress Free ta-C Coatings by means of Up-Scaled Pulsed Laser doped DLC coatings in micromachining of Ti6Al4V samples and compared Deposition for Industrial Applications, Hagen Gruettner to an uncoated tool, an increased tool performance was obtained. ([email protected]), D. Haldan, J. Maus, Hochschule B3-5 Preparation of Hybrid ta-C/MoS2-Films by using Laser Arc Mittweida - University of Applied Sciences, Germany; M. Nieher, Technology, Frank Kaulfuss ([email protected]), F. Hochschule Mittweida - University of Applied Sciences , Germany; S. Hofmann, Y. Han, F. Schaller, Fraunhofer IWS, Germany; T. Kruelle, Weissmantel, Hochschule Mittweida - University of Applied Sciences, Fraunhofer IWS,Germany; S. Makowski, V. Weihnacht, A. Leson, L. Lorenz, Germany M. Zawischa, Fraunhofer IWS, Germany In many industrial applications highly wear-resistant coatings are required Hydrogen-free ta-C coatings are already used to reduce friction in to protect and / or functionalize tools and components. While typical lubricated environments. The application under minimum quantity representatives of DLC coatings are already in large-scale industrial use, lubricated and non-lubricated boundary conditions remains a great stress free ta-C coatings produced at the Laser Institute Mittweida (LHM) challenge. The addition of the dry lubricant MoS2 is intended to improve by means of a patented combination of pulsed laser deposition and pulsed the performance characteristics of the ta-C in this case. For the production laser stress relaxation are currently well under way due to their of ta-C coatings, the Laser Arc process is particularly suitable, with which On Demand available April 26 - June 30, 2021 7 On Demand available April 26 - June 30, 2021 very hard and low-defect coatings can be produced. MoS2 targets can be Hard Coatings and Vapor Deposition Technologies combined and alternately evaporated using the same technique. Room On Demand - Session B4 By adapting the discharge conditions, ta-C/MoS2 layers could be produced in different variants. In addition to ta-C with simple MoS2 top layer, Properties and Characterization of Hard Coatings and multilayers with alternating deposition were also produced with single Surfaces layer thicknesses in the nanometer range. The plasma states of the components, which have a large influence on the layer formation, were B4-1 Investigating the Influence of Nanocomposite Structure on the investigated as well as the cathode spot behaviour at the different Thermal Stability of Ag in VSiCN-Ag Coatings, Forest Thompson ([email protected]), South Dakota School of Mines and materials (graphite, MoS2). The investigations also concentrated on the mechanical properties of the layers, which were determined by SEM, TEM, Technology, USA; F. Kustas, NanoCoatings, Inc., USA; G. Crawford, South X-ray diffraction, nanoindentation and scratch testing. In addition, Dakota School of Mines and Technology, USA tribological tests provide information on the influence of the layer Self-lubricating coatings have been studied extensively for elevated structure in different applications. temperature tribological applications. For coating designs in which a noble metal solid lubricant phase is continuously supplied to the surface from B3-6 Effects of Target Poisoning Ratios on the Microstructure, Mechanical within a ceramic-based matrix, control of noble metal out-diffusion can be Properties and Corrosion Resistance of WCx Coatings Fabricated by challenging. To investigate the potential of manipulating nanocomposite Superimposed HiPIMS and MF System, Igamcha Moirangthem, Ming Chi structure to better control solid lubricant stability and transport, VSiCN and University of Technology, Taiwan; S. Chen, National Taiwan University, VSiCN-Ag nanocomposite coatings were deposited by plasma-enhanced Taiwan; J. Lee ([email protected]), Ming Chi University of reactive magnetron sputtering. A nominal Ag content of 4 at.% was Technology, Taiwan maintained while amorphous phase content was varied with the intent of In this work, we studied the effect of target poisoning ratios of tungsten modifying coating density, grain size, and grain morphology. As-deposited carbide films using a superimposed HiPIMS and MF system. The flow rate coatings were characterized by energy dispersive X-ray spectroscopy, of the acetylene (C2H2) was controlled using a plasma emission monitoring scanning electron microscopy, X-ray diffraction, and transmission electron (PEM) system to feedback control the target poisoning ratio during microscopy. Hardness and apparent elastic modulus were measured by deposition. Five coatings, WC10, WC30, WC50, WC70 and WC90, were nanoindentation. The thermal stability of Ag within the coatings was grown under target poisoning ratios of 10%, 30%, 50%, 70% and 90% evaluated by inspection of the coating surfaces after vacuum annealing at respectively, on Si, AISI420 stainless steel (SS) and AISI304 SS substrates. A 550°C. Relationships among coating microstructure and Ag thermal stability small hysteresis loop area for the emission intensity of W at 429.6 nm was are identified and potential influences on coating performance in observed with variation of C2H2 gas flow rates. With increasing target tribological applications are discussed. poisoning ratios, the phases changed from nanocrystalline β-WC1-x to amorphous. The X-ray photoelectron spectroscopy was used to study the B4-2 Spinodal Decomposition of Reactively Sputtered VAlN Thin Films, chemical bindings of coating. The highest power normalized deposition Marcus Hans ([email protected]), H. Rueß, RWTH Aachen rate of 25.20 nm min-1kW-1 was observed for WC90. The highest hardness University, Germany; Z. Czigány, Centre for Energy Research, Hungary; J. value of 32.3 GPa was measured for WC30. WC50 showed the best Krause, P. Ondračka, D. Music, S. Evertz, D. Holzapfel, RWTH Aachen University, Germany; D. Primetzhofer, Uppsala University, Sweden; J. adhesion among the coatings with LC2 value of 65.1 N. The lowest COF of 0.26 was observed for WC90. In potentiodynamic polarization test using Schneider, RWTH Aachen University, Germany We investigate the decomposition mechanisms of metastable cubic (c– 0.1M H2SO4 solution, WC90 showed colourful fringes around the corrosion 2 )(V0.64Al0.36)0.49N0.51 thin films, grown by reactive high power pulsed micro-pits with the highest polarization resistance (Rp) of 4552.51 kΩcm . magnetron sputtering, by combination of structural and compositional Keywords: Superimposed high power impulse magnetron sputtering, characterization at the nanometer scale with density functional theory middle frequency, WCx coatings, tungsten doped diamond-like carbon (DFT) calculations. Based on thermodynamic considerations of d2G/dx2 < 0, coating, target poisoning, nanoindentation, tribometer spinodal decomposition is expected for c-V1-xAlxN with x ≥ 0.35. While no B3-7 The Influence of Different Power Supply Systems on the indications for spinodal decomposition are observable from laboratory and Microstructure, Mechanical and Corrosion Properties of Titanium Carbide synchroton diffraction data after annealing at 1300°C, the formation of Coatings, H. Yu -Tung, Ming Chi University of Technology, Taiwan, Republic wurtzite (w–)AlN is evident after annealing at 900°C by utilizing high energy of China; C. Li-Chun, Ming Chi University of Technology, Taiwan; L. Bih- synchrotron X-ray diffraction. However, the complementary nature of Show, Chang Gung University, Taiwan; Lee Jyh-Wei elemental V and Al maps, obtained by energy dispersive X-ray spectroscopy ([email protected]), Ming Chi University of Technology, Taiwan in scanning transmission electron microscopy mode, imply spinodal Titanium carbide (TiC) coatings have attracted wide attention from decomposition of c–(V0.64Al0.36)0.49N0.51 into V- and Al-rich cubic nitride researchers and industry due to their high hardness, good wear and phases after annealing at 900°C. These chemical modulations are corrosion resistance. In this study, the TiC coatings were fabricated by four quantified by atom probe tomography and maximum variations of x in V1– different power supply systems including superimposed HiPIMS-MF, xAlxN are in the range of 0.36 to 0.50. The magnitude of the compositional HiPIMS, MF, and DC in a gas mixture of acetylene and argon. During the modulations is enhanced after annealing at 1100°C as x varies on average deposition process, a plasma emission monitoring (PEM) system was used between 0.30 and 0.61, while the modulation wavelength remains to control the Ti target poisoning status to 70%. The single crystal silicon unchanged at approximately 8 nm. Based on DFT data, the local x variation wafers and AISI304 stainless steel plates were used as substrates. The from 0.30 to 0.61 would cause lattice parameter variations from 4.111 to chemical compositions of TiC films were analyzed by a field emission 4.099 Å. This difference corresponds to a shift of the (200) peak from 44.0 electron probe microanalyzer. The microstructure of thin film was to 44.1°. As the maximum decomposition-induced peak separation examined by a field emission scanning electron microscope. The crystalline magnitude of 0.1° is significantly smaller than the measured full width at structure of thin film was analyzed by an X-ray diffractometry. The half maximum of 0.4°, spinodal decomposition cannot be unravelled by hardness, adhesion and tribological properties of TiC films were evaluated diffraction data. However, consistent with DFT predictions, spinodal by nanoindenter, scratch test and pin-on-disk wear test, respectively. The decomposition in c–(V0.64Al0.36)0.49N0.51 is revealed by chemical composition characterization at the nanometer scale. corrosion resistance of TiC films in 0.1 M H2SO4 aqueous solution was examined by an electrochemical workstation. The influence of four B4-3 Effect of Functionally Graded Layers on Tribological Behavior of different power supplies on the deposition rate, microstructure, hardness, TiZrN Coatings on AISI D2 Steel, Jia-Hong Huang adhesion, wear and corrosion resistance of TiC films were studied in this ([email protected]), B. Tsai, National Tsing Hua University, Taiwan work. Although the deposition rate of the TiC coating deposited by DC The objectives of this study were to investigate the role of TiN transitional power supply was the highest, the film quality was inferior to other films layer and Ti interlayer in the tribological behavior of tri-layer TiZrN/TiN/Ti due to its less dense microstructure. On the other hand, the TiC coating coatings and to explore the mechanism of stress relief in the tri-layer fabricated by superimposed HiPIMS-MF power supply exhibited a dense coatings. TiZrN coatings were deposited on AISI D2 steel by DC unbalanced microstructure, good mechanical property and excellent corrosion magnetron sputtering. There were three series of samples, including single resistance. layer TiZrN (S), bilayer TiZN/Ti (B), and tri-layer TiZrN/TiN/Ti (Tx) in this study. The TiN thickness of Tx-series specimens ranged from 200 to 400 nm. The N/(Ti+Zr) ratios of TiZrN layer ranged from 0.9 to 1.0 and the Zr/(Zr+Ti) ratio of TiZrN coatings was about 0.5. The hardness of the On Demand available April 26 - June 30, 2021 8 On Demand available April 26 - June 30, 2021 specimens varied from 28.1 to 31.9 GPa which slightly decreased by Numerical results demonstrated a clear quantitative relationship between introducing TiN transitional layer. The residual stress of TiZrN layer the coating stiffness degradation and its damage accumulation. It was decreased from -8.56 to -3.28 GPa with increasing thickness of interlayer observed from a case study that first crack (0.01 µm in width and 0.05 µm and transitional layer. Scratch test was used to evaluate adhesion strength. in depth) was initiated at 8th loading cycle, and it propagated through the The results showed high Lc2 critical loads for all specimens ranging from coating thickness with increasing number of loading cycles reaching 1.4 µm 63.2 to 88.6 N. The TiN transitional layer could improve the adhesion at the 100th cycle. It was also noticed that the plastic deformation of the strength, and the Lc2 increased as the thickness of transitional layer hardened case developed significantly, which might be a major increased. The wear rate of the tri-layer coatings was lower than that of contribution of the initiation of the crack. TiZrN single layer and bilayer coatings. The results indicated that The results observed in this study are in agreement with our recent introducing the interlayer and transitional layer could enhance the wear experimental observations (Beake et al, 2019), which indicated that micro resistance. The wear rate almost linearly increased with increasing elastic crack/wear damage was occurring at the early stage of nano-indentation stored energy (Gs) that was related to elastic constants, residual stress and loading cycles. The numerical study confirmed, that once crack was coating thickness [1]. The difference between the fracture toughness (Gc) initiated, it propagated rapidly through the coating, which can lead to and Gs can be considered as the capability that the coating can absorb delamination when the crack reaches the hardened substrate interface. externally input energy. The increase of Gs may decrease the capacity in absorbing energy and thereby decreasing the wear resistance. Therefore, Key words: Fatigue failure; Cohesive Zone Model; Cyclic loading; Gs could be taken as an index to evaluate the wear resistance of coatings Reference [2]. Reference 1. Feng, J & Qin, Y (2012), Prediction of the critical load of a metal- [1] An-Ni Wang et al., Surf. Coat. Technol. 239(2014)20. rolling system by considering the damage of the coated surface, [2] Yu-Wei Lin et al., Surf. Coat. Technol. 350(2018)745. Steel Research International, Metalforming, Special Edition. 2. Beake, B.D., Isernm L., Endrino, J.L., Fox-Rabinovich, G.S., B4-4 Thin Film Characterization by Picosecond Ultrasonics on High (2019), Micro-impact testing of AlTiN and TiAlCrN coatings, Curvature Surfaces, Frederic Faese ([email protected]), J. Michelon, Wear, 418–419, 102-110. X. Tridon, Neta, France Since the discovery of picosecond ultrasonics by H. J. Maris and his team in B4-6 Microstructure and Oxidation Behaviour of Arc Evaporated TiSiN 1984, this nondestructive technique continuously expanded and found Coatings Investigated by in-situ Synchrotron X-ray Diffraction, Yvonne numerous applications. Where the first application concerned thin film Moritz ([email protected]), C. Saringer, M. Tkadletz, thickness measurement in the semiconductor industries with a complex Montanuniversität Leoben, Austria; A. Stark, N. Schell, Helmholtz-Zentrum setup, picosecond ultrasonics technique is now much more efficient, user- Geesthacht, Germany; M. Pohler, CERATIZIT Austria GmbH, Austria; N. friendly and widespread. Indeed, thickness measurement is now easily Schalk, Montanuniversität Leoben, Austria reachable and this technique also allows the elastic properties measurement of thin films, multilayers and nanostructures, adhesion TiSiN hard coatings are a suitable candidate as a protective layer for various properties evaluation, etc. Thus, among all the fields that are potentially cutting applications, due to their advantageous mechanical properties and interested in this new technique are mainly surface engineering, excellent oxidation resistance. Within this work, a detailed characterization microelectronics and biology. of the microstructure of TiSiN is complemented by the investigation of its oxidation mechanism using in-situ X-ray diffraction (XRD) at a synchrotron We will see how the photo-generation and the photo-detection of ultra- radiation facility. XRD, X-ray photoelectron spectroscopy and transmission high frequency ultrasounds (of the order of THz) can accurately and rapidly electron microscopy investigations of an as-deposited TiSiN coating grown measure the thickness of a TiN hard coating on a Ti substrate. This on cemented carbide substrate indicate the presence of a nanocomposite measurement can be performed either locally with a high spatial resolution structure, consisting of Ti(Si)N nanocrystallites embedded in an amorphous or by scanning the sample, hence giving a mapping of the thickness Si3N4 matrix. To illuminate the oxidation stability, a powdered coating was measurement on the whole surface. Up to now, the shape of the samples annealed in air between 100 and 1200 °C and the recorded 2D X-ray had to be very flat; in this presentation, we will demonstrate that we can diffractograms were correlated with the results of differential scanning also analyze even highly curved samples. Compared to concurrent calorimetry. Sequential Rietveld refinement of the obtained synchrotron techniques such as ellipsometry or the Calo tester, picosecond ultrasonics data provided temperature-dependent information about the phase presents the unique advantages to be contactless, nondestructive and able composition and thermal expansion of the individual phases. The results to evaluate the properties of a complex shape sample. To illustrate this last revealed an oxidation stability of TiSiN up to a temperature of point, results will be presented showing outstanding features such as an approximately 830 °C, followed by the formation of both, rutile and advanced 3D mapping of a hard coating thickness on a cylinder or a sphere. anatase TiO2. It was shown that the quantity of the metastable anatase B4-5 Fatigue Behaviour of Thin Coating and the Influences of Plastic phase reached its maximum at a temperature of 1020 °C and then Deformation of Harden-case using Irreversible Cohesive Zone Model, continuously transformed into the stable rutile modification at higher Jiling Feng ([email protected]), Manchester Metropolitan University, UK; temperatures. The present findings provide a detailed insight into the Y. Qin, University of Strathclyde, UK; T. Liskiewicz, Manchester complex microstructure and oxidation mechanism of TiSiN coatings, Metropolitan University, UK; B. Beake, Micro Materials Ltd, UK allowing to further optimize this system for future applications. Cohesive-zone modelling technique has been proved to be an efficient Keywords: TiSiN hard coatings, arc evaporated, Sequential Rietveld approach to simulate the fracture behaviour of multi-layered coatings refinement, oxidation resistance, TEM under monotonically loading (Feng, 2012). This paper aims to investigate B4-7 High Temperature Tribology of Hf Doped c-Al0.67Ti0.33N Cathodic Arc the fatigue failure mechanism of coating system by observing the PVD Coatings Deposited on M2 Tool Steel, G. Mondragón Rodríguez, procedure of initiation and propagation of cracks within the coating under Alvaro Enrique Gómez Ovalle ([email protected]), J. the cyclic loads. Alvarado Orozco, J. González Carmona, C. Ortega Portilla, J. Hernández We developed a “three-layer” finite element model, composed of the Mendoza, CIDESI, Mexico coating, hardened case and substrate, which was validated via nano- c-Al(1-x)TixN hard coatings are widely applied due to their thermal stability indentation technique with 300 µm radius indenter. Homogenous material up to 800 °C, high resistance to wear and oxidation. Due to these properties were assumed for both the TiN/CrN coating and the substrate, characteristics they are frequently deposited on cutting tools used for with multi-linear hardening behaviour. Prior to coating deposition, the machining processes. Improvements on the mechanical and oxidation substrate was heat-treated by plasma nitriding to enhance the load-bearing properties are derived from the microstructure characterized by a stable capacity of the coating/substrate system. solid solution of Al in TiN. In the present research, undoped a) c-Al0.67Ti0.33N An irreversible cohesive constitutive equation, taking into account the and hafnium doped b) c-Al0.67Ti0.33HfxN, which were deposited using the energy dissipation resulted from frictional interaction of asperities along cathodic arc technique using 500 sccm of high purity N2, Temperature = the cohesive surfaces and crystallographic slip, was employed to identify 430 °C, Pressure = 8 x 10-2 mbar, deposition time = 400 Ah, cathode the crack initiation and to simulate the crack propagation under the cyclic current = 150 A and bias voltage = -80 V. The elemental chemical analysis loads. An in-house User Material (UMAT) subroutine was used to simulate displays hafnium contents ranging from 1.0 to 2.26 wt. %. The scanning the degradation of coating material upon cyclic loading. electron microscopy analysis of the surface of both coatings showed similar On Demand available April 26 - June 30, 2021 9 On Demand available April 26 - June 30, 2021 droplets sizes and defects density produced by the cathodic arc deposition. oxidation resistance were furthermore studied in detail by differential Through the grazing incidence X-ray diffraction (DRX), the characteristic scanning calorimetry and thermogravimetric analysis in inert atmosphere peaks of a cubic Al1-xTix N coating were observed for both the reference and in synthetic air to enlighten the origin of the mechanical and structural coating and the doped nitride. Tribology tests of the c-Al0.67Ti0.33HfxN stability at elevated temperatures. The results show that especially high Si- coating in an argon jet for 250, 500, 1000, 2500 & 5000 cycles at a containing AlCrSiN coatings with Al/Cr ratios higher than 80/20 exhibit temperature of 900 °C showed the evolution and wear behavior under excellent oxidation resistance with negligible mass gain up to 1250 °C. these conditions. The predominant friction mechanisms observed were The combinatorial approaches used within this study are powerful in related to abrasion, showing that hard particle formation and plowing seeking perspective coatings with specific elemental and phase increased wear with increasing distance. Oxidation prevents from further compositions and can be effectively applied also in industrial-sized debris formation, while at room temperature debris are oxidized due to deposition systems. Moreover, they enable to understand various friction. The friction coefficients were maintained after the inclusion of mechanisms responsible for high thermal stability and oxidation resistance hafnium as a doping material, however high temperature wear was of coatings while combined with modern characterization methods. reduced. These observations correlated well with the transition and stable oxide phases being formed at 900 °C during the tribology tests. B4-10 In-plane Texturing of Silver Thin Films, Francesca Corbella Keywords: Hf doped, tribology, high temperature tribology, arc PVD. ([email protected]), Saint-Gobain Recherche/CNRS, France Pollution and energy waste are main concerns for today's society. In B4-8 Cross-sectional X-ray Nanodiffraction Characterization of Radiation buildings, part of the waste is due to thermal radiation losses through Damage, Stresses, and Microstructure in Tungsten Coatings, Kostiantyn windows1. To address the problem, low-emissive coatings were introduced Hlushko ([email protected]), Montanuniversität in the market. By being reflective in the far IR range and transmissive in the Leoben, Austria; A. Mackova, Nuclear Physics Institute of the Czech visible light, the low-emissive coatings are designed to reduce the heat Academy of Sciences; J. Todt, Erich Schmid Institute for Material Science, losses from inside the building to the outside, while maximizing the solar Austrian Academy of Sciences, Austria; R. Daniel, Christian Doppler gain. Such properties are achieved through silver based multilayers, Laboratory for Advanced Synthesis of Novel Multifunctional Coatings at the deposited on the glass through a PVD process. The efficiency of the Department of Materials Science, Montanuniversität Leoben, Leoben, coatings is then related to the maximization of the IR reflectance, which Austria; J. Keckes, Montanuniversität Leoben, Austria depends on the electrical conduction of the nanometric silver layer.2 The A better understanding of depth-dependent radiation damage in protective minimization of the Ag resistivity becomes, therefore, a key point for coatings which can be used in fusion/fission reactors and in space is enhancing the optical properties of the coatings. In thin films, the essential pending step for further development of novel coating types and conductivity of a material depends on its structural properties, which are microstructures that are capable of withstanding severe environments over influenced by its seed layer. Till today, ZnO was recognized as the best long time periods. Tungsten is a perspective material for plasma-facing underlayer for Ag and the most used oxide in the industrial glazing. In components of a fusion reactor due to its high radiation resistivity, high particular, it was observed that the deposition of the oxide in its textured thermal conductivity and high melting point. In this contribution, 8µm thick hexagonal lattice led to the growth of a Ag (111) out-of-plane textured film, nanocrystalline tungsten coating on WC substrate with columnar with enhanced electrical properties. Film texturization can play an microstructure was irradiated using Si2+ ions with an energy of 5MeV with a important role on silver conductivity.4-5 Starting from a model ZnO single fluence of 2x1016 ions/cm2.In order to investigate depth-dependent crystal based stack, our study showed the impact of in-plane and out-plane changes in residual stresses and microstructure induced by the irradiation, texturization on silver resistivity . The system was then optimized with the cross-sectional X-ray Nanodiffraction (CSnanoXRD) with a beam size of 100 introduction of a buffer polycrystalline ZnO layer, showing promising nm was applied at European Synchrotron Radiation Facility in Grenoble, results. The ultimate goal is to reproduce the structural and electrical France, to scan 50µm samples at the film cross-section. The experimental properties, observed on the single crystal stacks, in polycrystalline results revealed significant changes in the depth-dependent gradients of sputtered coatings through Ion Beam Assisted Deposition, a sputtering residual stresses as well as with the changes in unstressed lattice technique becoming more and more suitable for an industrial parameters, which will be presented together with the data from implementation. transmission electron microscopy. [1] « Couches conductrices transparentes. Applications aux vitrages isolants B4-9 Combinatorial Approach for the Synthesis of Thermally Stable High et aux vitrages actifs. » Cours (2011) Si-containing Nanocomposite AlCrSiN Coatings, Michal Zítek [2] E. Hagen and F. Rubens, Annalen der Physik 11, 873 (1903) ([email protected]), N. Jäger, M. Meindlhumer, [3] M. Philipp, PhD thesis, Universitât Dresden and UPMC (2011) Montanuniversität Leoben, Austria; F. Nahif, voestalpine eifeler-Vacotec GmbH, Düsseldorf, Germany; C. Mitterer, R. Daniel, Montanuniversität [4] D Köhl, PhD thesis, RWTH Aachen University (2011) Leoben, Austria [5] R. Sittner, Ag workshop Paris, “Impact of diverse growth templates on High-performance cutting tools are subjected at high cutting speeds to high the growth of Ag thin films” (2015) loads and temperatures typically exceeding 1000 °C. AlCrN alloyed with Si B4-12 INVITED TALK: Modern Analytical Methods for Characterizing the has been shown to be a perspective coating system for protection of Tribological Material Properties of Coatings, Dietmar Schorr cutting tools operating in such harsh industrial environments as it exhibits ([email protected]), Cooperate State University in promising mechanical properties and thermal stability. Especially low Si- Karlsruhe, Germany INVITED containing AlCrN coatings are known for their enhanced mechanical This paper presents photothermal principle as a new method for properties as well as improved thermal stability and oxidation resistance determining the tribological properties of hard coatings. The coating due to their nanocomposite structure. properties, which determine the friction and wear behaviour of a Unlike Si concentrations far below 10 at.% Si, which are frequently tribological system, are the coating thickness, the adhesive strength and reported in literature, the focus of this work is to systematically study arc- the hardness. The known classical analysis methods have disadvantages in evaporated AlCrSiN coatings with a high Si content of about 15 at.%, determining the respective coating properties and are not applicable for varying the Al/Cr ratio from 50/50 to 90/10. Elemental composition was many coatings and surfaces. Furthermore, these methods only provide controlled by co-evaporation of (Al50Cr50)75Si25, (Al70Cr30)75Si25 and information on the individual coating properties, but not on the overall (Al90Cr10)75Si25 cathodes in an industrial-sized deposition system (alpha400P, tribological behaviour of a coating. With the photothermal method, these voestalpine eifeler Vacotec GmbH). This combinatorial approach allowed limits are exceeded and it also works where classical methods fail. for a synthesis of coatings with a wide range of elemental composition Photothermics works non-destructively and can be used to determine the from Al19Cr21Si16N44 to Al30Cr5Si16N50. coating properties over a wide area. The photothermal technology works XRD measurements revealed that the AlCrSiN coatings display a with thick and thin layers, for cohesive and adhesive adhesion testing and nanocomposite structure consisting of a mixture of cub-CrN and hex-AlN is independent of surface roughness. phases. The observed gradual increase of the Al/Cr ratio led to an In photothermal peripheral zone analysis, an intensity-modulated laser increasing compressive residual stress and fraction of softer hex-AlN phase. spot hits an object surface. The radiation is absorbed on the surface and These two competing mechanisms resulted in hardness of about 25 GPa generates a heat flux that propagates into the interior of the component in irrespective of the coating composition, which was preserved even after the form of thermal waves. The waves have the same frequency as the annealing at 1000 °C in vacuum. That makes this coating system interesting irradiated laser light. The further propagation of the thermal waves is for various high-temperature applications. The thermal stability and influenced by the thermal properties of the coating (thermal diffusivity). On Demand available April 26 - June 30, 2021 10 On Demand available April 26 - June 30, 2021 These cause the waves to be reflected back and radiated at the surface as film growth mechanism was discussed in terms of deposition parameters, heat. The thermal resistance of the material ensures that the thermal including gas mixture and sputtering power density. The distinguishable waves travel through the material with a time delay and that the phase of interfaces in the multilayers could be established by different the radiated heat is offset from the radiated laser. If the thermal properties microstructure of adjacent layers. The higher power and larger N2 gas inlet of the coating change due to thickness, hardness or adhesion strength, this during deposition generated amorphous layers and suppressed the is measured by the phase shift. This is also almost independent of the continuous growth of columnar crystals in crystalline layers. In addition, surface roughness. the high power impulse method was also employed to modify the The reflected waves are registered by an infrared detector, which is cooled interfaces between building layers. The intact and flattened interfaces down to increase sensitivity. The penetration depth of the oscillating were beneficial to the discontinuity of the microstructure of the building thermal waves into the interior of the material is determined by the layers for the single transition metal nitride multilayer coatings. modulation frequency of the laser and depends on the thermal properties B4-18 Numerical Evaluation of the Contact Fatigue Resistance of AlCrN, N of the material. High frequencies in the kHz range are used for layer and AlCrN/N Coatings on AISI 4140 Steel, Andre Ballesteros-Arguello analysis and low frequencies in the Hz range for material analysis. ([email protected]), F. Ramírez-Reyna, A. Meneses-Amador, B4-14 INVITED TALK: Metal Oxynitride Thin Films: A Review on Synthesis G. Rodríguez-Castro, D. Fernández-Valdés, O. Reyes-Carcaño, National Developments, Performance, and Applications, Sharafat Ali Polytechnic Institute, Mexico ([email protected]), Linnaeus University, Sweden INVITED An experimental-numerical study of the contact fatigue resistance of This talk will provide an overview of the latest research development on coatings over an AISI 4140 steel was developed. Three experimental metal containing nitrogen rich oxynitride thin films as hard, durable and conditions were carried out: a coating of aluminum chrome nitrides (AlCrN) strong material. I will start giving an overview of silicon oxynitride thin, by physical vapor deposition process (PVD), a coating of iron nitrides (N) by preparation of these films by different techniques and variation of gas nitriding process and finally a multilayer system of AlCrN/N. Contact properties with the N content. I will also talk about the new amorphous fatigue tests were performed on a MTS Acumen electrodynamic test thin films in the metal containing -Si-O-N systems containing a high amount system in charge controlled mode, by cyclic loading of a sphere on a flat of nitrogen and metals. Recently we have deposited novel AE-Si-O-N thin- surface formed by the layer-substrate system. The contact fatigue test film materials (AE= alkaline earth e.g. Mg, Ca, and Ba), onto float glass methodology consisted of two main stages. First, critical loads were surfaces, by magnetron sputtering. Mechanical and physical properties determined under monotonic loads, for each of the systems, where show hardness values up to 22 GPa, reduced elastic modulus values up to circumferential cracks were considered as the failure criterion. Second, 175 GPa and refractive index values up to 2, which can be compared to the fatigue conditions were performed in a low cycle using subcritical uncoated float glass having hardness of 7 GPa, elastic modulus of 65 GPa monotonic loads with a frequency of 5 Hz. A numerical model based on the and refractive index of 1.50. These thin films can be potentially used as a finite element method was developed to evaluate the stress field protective cover for displays and touch screens in tablets, smartphones, generated in the systems by cyclic contact loads. The results exhibit a watches, etc. better resistance to contact fatigue in the AlCrN/N multilayer system, due to the presence of the intermediate layer of iron nitrides. B4-16 Influence of the Period of the Substrate Oscillation on Thin CrN Films Obtained by RF Physical Vapor Dynamic Glancing Angle Deposition B4-19 Low Temperature Deposition of TiB-based Hard Coating Films by Technique, M. Jimenez, F. Cemin, A. Riul, L. Zagonel, UNICAMP, Brazil; C. Pulsed DC Plasma CVD, Takeyasu Saito ([email protected] Figueroa, Universidade de Caxias do Sul, Brazil; D. Wisnivesky, UNICAMP, u.ac.jp), H. Matsushima, K. Fuji, D. Kiyokawa, N. Okamoto, Osaka Brazil; Fernando Alvarez ([email protected]), Instituo de Física- Prefecture University, Japan UNICAMP, Brazil Cemented carbide is often used for molds and cutting tools based on high The control of the physical properties of hard metallic nitride coatings is hardness (1800 Hv for WC, 1200-1500 Hv for WC-Co) and toughness (4-6 1/2 1/2 mandatory to obtain good performance in applications such as cutting Mpa・m for WC, 13-20 Mpa・m for WC-Co ), in which Ti-based hard tools. In this work, nanostructured chromium nitride (CrN) films are coating films are generally used to improve functions such as hardness, obtained by combining radio frequency magnetron sputtering (RFMS) and heat resistance, durability, releasability and lubricity. Typical Ti-based hard dynamic glancing angle deposition (DGLAD) using Programmable Logic films are TiC, TiN and TiCN, in which TiCN has advantages of TiC with high Controller (PLC). By appropriate choosing the substrate oscillation hardness (3000-3800 Hv) and low friction coefficient (0.1) and TiN with frequency, the physical properties such as micro and nanostructure, excellent oxidation resistance (ca. 600ºC). In addition, TiB2 has excellent morphology, hardness, texture, and crystallite size are feasible to be heat resistance, oxidation resistance (over 400ºC), and high hardness (20- tailored. Samples are deposited by moving the substrates forward and 70 GPa). However, it is difficult to form TiB2 thin film with high growth rate backward (-φ0 < φ(t) < +φ0) by controlling the angular velocity ω = dφ/dt, and good crystallinity at low temperatures. It is important to deposit TiB2 inducing the formation of wavy-like periodic columnar nanostructures. coating films with good crystallinity to get enough hardness, by controlling Herein, we explore the effects prompted by the substrate oscillations at the ratio of Boron, Carbon and Nitrogen, to balance the superior relatively short periods (1

On Demand available April 26 - June 30, 2021 11 On Demand available April 26 - June 30, 2021 the dissociation reaction in the plasma and the accumulation of charges on calculated; however, experimental synthesis of only crystalline Mo2BC was the substrate surface. reported so far [2,3]. Apart from post-deposition annealing [3], HiPIMS was shown to be an effective way to prepare crystalline Mo2BC at industrially relevant deposition temperatures [2]. Other X2BC such as W2BC have been Hard Coatings and Vapor Deposition Technologies predicted to exhibit better mechanical properties compared to Mo2BC, Room On Demand - Session B5 however, this comes at the cost of near-zero formation enthalpy predicting problems with the crystallization of this phase. On the other hand, systems Hard and Multifunctional Nanostructured Coatings such as Nb2BC should exhibit lower hardness and ductility, but they should be significantly easier to be synthesized in the correct crystalline form. B5-1 INVITED TALK: PVD of Hard Nanocomposite Coatings Using This contribution reports on HiPIMS driven deposition of different X2BC Multiphase SHS Cathodes - Evolution and New Horizons, Philipp Kiryukhantsev-Korneev ([email protected]), E. Levashov, systems covering systems with low as well as higher negative formation enthalpies. Coatings prepared at ambient temperature as well as those National University of Science and Technology "MISiS", Russian Federation prepared elevated temperatures > 700 °C will be compared. The INVITED correlation between the deposition parameters, the structure of the The development of PVD technologies is often related with creation of new coatings and their mechanical properties will be shown. multicomponent materials that are used as precursors in deposition process. Particularly relevant is the manufacture of cathodes made of This research has been supported by the project LO1411 (NPU I) funded by ceramics & composite materials. Since the doping of coatings by structure Ministry of Education, Youth and Sports of Czech Republic, project modifiers, such as B or Si, for example, is a non-trivial task. Among the CZ.1.05/2.1.00/03.0086 funded by the European Regional Development methods of ceramic cathodes manufacturing can be noted the Fund and GACR project 15-17875S. pressing+sintering & hot pressing technology. Self-propagating high- [1] H. Bolvardi, J. Emmerlich, M. to Baben, D. Music, J. von Appen, R. temperature synthesis (SHS) is the cost effective & convenient method for Dronskowski, J.M. Schneider, J. Phys.: Condens. Matter 25 (2013) 045501 manufacturing of composite cathodes [1]. [2] H. Bolvardi, J. Emmerlich, S. Mráz, M. Arndt, H. Rudigier, J.M. Schneider, The SHS method allows obtaining a wide range of materials & cathodes Thin Solid Films 542 (2013) 5-7 have a high density & a low content of impurities due to self-cleaning effect [3] L. Zábranský, V. Buršíková, P. Souček, P. Vašina, J. Dugáček, P. Sťahel, J. in the combustion wave. In present review, the several types of advanced Buršík, M. Svoboda, V. Peřina, Vacuum 138 (2017) 199-204 coatings deposited with the SHS-materials were demonstrated. It was shown that the follow nanocomposite coatings can be produced in B5-4 Ammonium Thiosulfate Precursor for Coating Molybdenum Disulfide various energy regimes, including rigid, due to the use of functionally onto the Surface of Porous Metal for High Anti-Wearing Application in the graded & reinforced SHS-materials (FGM & RM): Machinery Industry, Lung-Hao Hu ([email protected]), National Sun Yat-Sen University, Taiwan; P. Chen, Southern Taiwan a) hard oxidation resistant MoHfSiB, MoZrSiB, & TaZrSiB coatings were University of Science and Technology, Taiwan obtained by DC magnetron sputtering (MS) & pulsed MS of (MoSi2-HfB2- High anti-wearing capability of friction coating is extremely important to MoB)/Mo, (MoSi2-ZrB2-MoB)/Mo, & (ZrB2-TaSi2)/Mo FGM disk targets [2] b) any low friction and machinary industry, especially for highly automated hard optically transparent TaSiCN coatings - by MS of TaSi2-TaC-SiC-Si3N4 production era coming, ”Industry 4.0”. Molybdenum disulfide (MoS2) RM disk targets c) hard corrosion resistant CrB2 & TiAlNiCN coatings - by belongs to Transition-metal dichalcogenids, TMDs . It is composed of HIPIMS using CrB2 & TiC-NiAl disk targets [3]. d) hard wear resistant TiCrBN layered structures, providing excellent wear resistance due to layer sliding . coatings - by ion implantation (MEVVA) or pulsed cathodic arc evaporation In this study, a cheap and massive producible ammonium thiosulfate (PCAE) of (TiB-Cr4Ti9B-Cr2Ti )/(Ti+TiB) ring FGM targets [4]. e) hard oxidation precursor ((NH4)2MoS4) has been developed for coating MoS2 layer onto & corrosion resistant coatings - by PCAE method using CrB2 & Cr3C2-NiAl the nano-porous anodic aluminum oxide (AAO) layer on the surface of rod targets. f) hard TiAlSiCN & TiCrSiCN coatings with high thermal 7003 series aluminum alloy. MoS2 layer on the aluminum alloy surface is stability/oxidation resistance - by MS of TiAl3-TiC-Ti5Si3-AlN & TiC-Cr3C2- detected by scanning electron microscope (SEM). The ammonium Ti5Si3 disk targets at high currents [5]. g) hard wear resistant soft magnetic thiosulfate precursor is pyrolyzed at 280, 375, 400 and 550°C, respectively FeTiB films - by MS of Fe/TiB2 segment target [6] h) hard oxidation resistant to form the MoS2 layer. The wearing experiment is tested by using the SiBCN films - by ion sputtering (IS) & MS of SiC-B4C disk SHS-targets [7]. Surface Hardness Abrasion Tester. After 1440 m wear test, the wear rates The research was carried out under the financial support of the Russian (weight loss/original weight) of pure 7003 aluminum alloy, AAO and MoS2 Science Foundation in the framework of project No. 19-19-00117. coated aluminum alloy pyrolyzed at 400°C are 0.339%, 0.017%, 0.0109%, 1. E.A. Levashov et al. Int Mater Rev 62 (2017) 203 respectively. The thickness of the molybdenum disulfide film sliced and 2. Ph. Kiryukhantsev-Korneev et al. Corros Sci 123 (2017) 319 observed by focused ion beam-transmission electron microscope (FIB-TEM) is about 40 nm. The surface hardnesses of AAO and MoS2 coated aluminum 3. Ph. Kiryukhantsev-Korneev et al. Ceram Int (2019) alloy are 3~4 GPa and 5~6 GPa, respectively, measured by doi.org/10.1016/j.ceramint.2019.09.152 nanoindentation. As the result of the test, the coating of MoS2 layer on the 4. Ph. Kiryukhantsev-Korneev et al. J. Phys.: Conf. Ser. 1238 (2019) 012003 surface of aluminum alloy substantially enhances anti-wear capability and 5. K. Kuptsov et al. Acta Mater 83 (2015) 408 hardness. This coating technique is expected to be used in all kind of metal parts for improving the lifetime of automated equipment . 6. E. Sheftel et al. Phys Status Solidi 13 (2016) 965 7. Ph. Kiryukhantsev-Korneev et al. Prot Met Phys Chem 53 (2017) 873 B5-5 Optimization of TiSiCN Coating Properties Obtained by RF Magnetron Sputtering and High Power Impulse Magnetron Sputtering, B5-3 On the Structure and Mechanical Properties of X2BC Coatings Joël Matthey ([email protected]), Haute Ecole Arc Ingenierie HES- Prepared by High Power Impulse Magnetron Sputtering at Different SO, Switzerland Ecole Arc Ingenierie, Switzerland; O. Banakh, R. Constantin, Temperatures, Pavel Soucek ([email protected]), M. Polacek, L. F. Bisoffi, M. Erard, Haute Ecole Arc Ingenierie HES-SO, Switzerland Zabransky, M. Stupavska, P. Vasina, Masaryk University, Brno, Czech Recently, remarkable properties of the TiSiCN coatings namely low friction Republic and good wear protection have been reported. Our study aimed at a As the demands for the quality and speed of machining increase, the comparison between different technologies (RF Magnetron Sputtering and application of protective coatings on cutting or forming tools becomes High Power Impulse Magnetron Sputtering) used for the coating increasingly important. Currently used protective coatings exhibit sufficient depositions. Operating in RF mode, a composite target Ti-Si-C was hardness, but this trait is often coupled with distinct brittleness. Recently a sputtered in Ar + N2 atmosphere. In HiPIMS mode, the coatings were material combining seemingly mutually exclusive high hardness and obtained from alloyed TiSi targets with different Si contents (15 and 25 moderate ductility has been theoretically predicted [1]. This material at.%) in a gas mixture containing Ar + N2 + C2H2. Tailoring the coating contains atoms of a transition metal (X), boron (B) and carbon (C) in X2BC properties can be successfully performed with a help of the target ion- stoichiometry ordered in a complex high aspect ratio unit cell. The induced secondary electron emission (ISEE). Technical aspects of both arrangement of the unit cell provides for high hardness of the material due technologies will be discussed in order to set a relationship between thin to strong ionic-covalent bonds together with enhanced ductility owing to film properties and process parameters. Physicochemical analyses (XRD, planes with only metallic bonds providing for plastic deformation of the SEM, XPS and RBS) were carried out to evaluate the coating composition, cell. The properties of X2BCs with different transition metals were morphology and crystalline structure. Residual stresses were determined

On Demand available April 26 - June 30, 2021 12 On Demand available April 26 - June 30, 2021 by the curvature method on glass plates. Nanohardness values up to 28 B5-8 Tuning Fracture Characteristics of Superhard Tm Carbide Coatings by GPa and Young’s modulus values up to 216 GPa were obtained while the Nitrogen Alloying, Thomas Glechner ([email protected]), R. coefficient of friction exhibited values below 0.35 against steel in an Hahn, TU Wien, CDL-SEC, Austria; D. Primetzhofer, Uppsala University, unlubricating pin-on-disk setup. The process parameters have been Sweden; H. Zaid, S. Kodambaka, University of California Los Angeles, USA; optimized to maximize the ion bombardment of the substrate surface by a D. Holec, Montanuniversität Leoben, Austria; P. Mayrhofer, TU Wien, monitoring the bias current signal with a Rogowski coil probe. The coating Austria; S. Kolozsvári, Plansee Composite Materials GmbH, Germany; J. thickness was set to one micron onto polished steel substrates. Ramm, Oerlikon Balzers, Oerlikon Surface Solutions AG, Liechtenstein; H. Riedl, TU Wien, CDL-SEC, Austria B5-6 Characteristics of Hf(M)SiBCN (M = Y, Ho, Ta, Mo) Coatings: Role of Cubic transition metal (TM) nitrides and carbides are well-established the M Choice, Martin Matas ([email protected]), M. Prochazka, J. protective coating materials due to their specific combination of Vlcek, J. Houska, University of West Bohemia, Czech Republic remarkable thermo-mechanical properties but also chemical inertness. Thin films based on light main group elements are attractive due to a Nevertheless, their unique bonding nature – in particular combination of unique combination of properties ranging from high hardness through strong covalent and metallic bonds – is also the origin for their lack in optical transparency to high–temperature stability and oxidation fracture tolerance compared to metals and metallic alloys. resistance. The properties, in the first place electrical conductivity, can be further modulated by addition of early transition metals. Properties of To overcome these limitations the formation of carbonitrides by amorphous Hf(M)SiBCN films are investigated by combining their substitutional alloying of the non-metallic sublattice exchanging C with N preparation using pulsed magnetron sputtering of boron–rich composite atoms is an interesting approach. The so obtained adjustment of the valence electron concentration has strong consequences on intrinsic targets B4C–Hf–M–Si (45–65% B4C, 15–20% Hf, 5% Y/Hf/Ho/Ta/Mo, 15– material properties, e.g. Young’s modulus, melting temperature, phase 30% Si) in 85% Ar + 15% N2 discharge gas mixture with ab-initio calculations. First, we study the effect of the M choice and fraction on decomposition as well as fracture toughness. Therefore, within this study the impact of non-metallic alloying – exchanging C with N atoms – has been calculated mechanical properties and formation energy (Eform) of binary MN explored systematically for two model systems, TaC and HfC, respectively. and ternary HfxM1–xN crystals. We discuss the dependence of Eform on the crystal structure and on the distribution of Hf and M in the metal TM-C thin films were deposited via non-reactive magnetron sputtering, while ternary TM-C-N coatings have been deposited in mixed Ar/N2 sublattice. The calculated mechanical properties of MN (rather than HfxM1– atmospheres. We combined ab initio calculations (DFT by VASP) with xN) very well correlate with measured mechanical properties of a– HfMSiBCN. The driving force towards N incorporation, monotonically experimental studies to correlate predicted properties such as fracture decreasing with increasing periodic-table group number of M according to tolerance enhancement with increasing VEC (due to nitrogen alloying). The mechanical characteristics have been assessed by micro cantilever bending, the calculated Eform of MN, very well correlates with measured electrical conductivity and extinction coefficient of a–HfMSiBCN. Second, we use ab– pillar compression or splitting tests in correlation to well-established initio molecular dynamics to model the a–HfMSiBCN materials of nanoindentation to gain a comprehensive view on the mechanical experimental compositions and densities themselves. The calculated band characteristics – also at elevated temperatures. Furthermore, detailed gap, localisation of states around the Fermi level and bonding preferences insights on the phase formation during coating synthesis (also considering of the M element (in particular the tendency of the M element to bind with influence of structural defects such as vacancies), and hence morphology N) also correlate with the measured increasing metallicity with respect to as well as chemical composition has been studied via ERDA and SEM/HR- the periodic-table group number of M, and confirm the possibility of TEM, respectively. predicting the trends of characteristics of a–HfMSiBCN using those of MN. B5-9 Improved Ti–Al–Ta–N Coatings by Doping with LaB6 and CeSi2, Third, we study the a–HfMSiBCN properties as a function of each other, Alexander Kirnbauer ([email protected]), S. Kagerer, TU and we identify an optimum target composition (B4C covered by 15% Hf, Wien, Institute of Materials Science and Technology, Austria; P. Polcik, 5% Ta and 15–20% Si) leading to hard (>20 GPa) films with relatively high Plansee Composite Materials GmbH, Germany; P. Mayrhofer, TU Wien, conductivity at a given extinction coefficient and vice versa. The results are Institute of Materials Science and Technology, Austria important for the design of hard, conductive and/or transparent high– The ever-growing need for improved mechanical and thermal resistance of temperature coatings. protective coatings ask for their continuous enhancement and B5-7 Thermal Stability of Nanostructured TiAl(Si,B)N Coatings Deposited optimization. Recently, we showed that CeSi2 or LaB6 doping (<2 mol%) of by HiPIMS with Positive Pulses, Álvaro Méndez Fernández well-known and used Ti–Al–N coatings leads to a considerable ([email protected]), J. Santiago, I. Fernández-Martínez, A. enhancement of their thermomechanical properties and oxidation Wennberg, Nano4Energy SL, Spain; M. Panizo-Laiz, Universidad Politecnica resistance. The very positive effects of Ta for Ti–Al–N (with Ta/Ti ratios of de Madrid, Spain; M. Monclús, J. Molina-Aldareguia, IMDEA Materials ~1/3) are already well documented. Within this study, we further follow Institute, Spain the alloying concept by preparing sputtered nitride coatings using In recent years, due to the advancement of high-speed machining (HSM), Ti0.45Al0.45Ta0.10 composite targets alloyed with 2 mol% CeSi2 or 1 mol% CeSi2 more demanding specifications on cutting tool coatings' hardness, chemical plus 1 mol% LaB6. The thereby developed single-phase face centered cubic inertness materials, wear resistance, anti-abrasion, and also thermal and LaB6 and CeSi2 doped Ti–Al–Ta–N coatings outperform the previously oxidation resistance are required. In order to overcome the detrimental studied Ti–Al–Ta–N coatings considerably. effects associated with high temperatures during HSM on tool life and In their as-deposited condition, the LaB6+CeSi2-doped Ti0.44Al0.42Ta0.13N workpiece surface finishing, nanostructured coatings based on multilayers coatings exhibit a hardness (H) of 37.8±1.5 GPa and an indentation or nanocomposites have been proposed [1, 2]. In this work, we present modulus (E) of 498±14 GPa (on polished sapphire substrates). Although the nanostructured TiAlSiN and TiAlBN coatings deposited by HiPIMS with hardness after vacuum-annealing at 1100 °C is with 30.7±1.8 GPa below positive pulses. The optimization of the coatings was carried out by that of the solely LaB6-doped Ti0.43Al0.57N (39.6±1.3 GPa), the oxidation tailoring metal ion fluxes and energies. More energetic process conditions resistance is simply outstanding. Even after exposure to ambient air at 900 have been provided by adjusting height and width of positive pulses. °C for 25 h, the oxide scale thickness is only 800 nm. Thus, easily Coatings’ microstructure has been studied and related to HiPIMS outperforming the solely LaB6-doped Ti0.43Al0.57N, but also the already parameters. The influence of Si and B from 0 to 15% at. content on excellent oxidation resistance of Ti0.44Al0.44Ta0.12N and Ti0.43Al0.42Ta0.14Ce0.01N, stabilizing fcc-AlN phase results has also been studied. The formation of which showed 2.4 and 1.9 µm thick oxide scales after 25 h exposure at 900 nanocrystalline grains (TiAlN) embedded in an amorphous phase (a-Si3N4, °C in ambient air, respectively. a-BN) provides enhanced toughness and wear resistance. Hardness up to Based on our results we can conclude that knowledge-based alloying 40 GPa were measured by nanoindentation techniques and high adhesion design is a powerful tool to meet the ever-growing demands of highly- critical load values were obtained in nanoscratch testing. High temperature sophisticated applications. nanoindentation and micropillar splitting were used to evaluate toughness and thermal resistance of the coatings. B5-10 Dislocation Confinement in Core-Shell Nanostructures: A Molecular [1] J. Musil, Surface and Coatings Technology 125 (2000 ) 322–330 Dynamics Study, Drew Fleming ([email protected]), Arkansas State University, USA [2] P. Mayrhofer et al., Progress in Materials Science 51 (2006) 1032–1114 Recently, a novel nanostructured surface composed of patterned arrays of Al/a-Si core-shell nanostructures (CSNs) has been shown to have a desirable combination of ultra-low friction (COF ~0.015 against a diamond counter face) and high durability. When subjected to instrumented On Demand available April 26 - June 30, 2021 13 On Demand available April 26 - June 30, 2021 nanoindentation, the individual CSNs show an unusual mechanical Design rules are uncovered that establish the phase boundaries classifying response characterized by almost complete deformation recovery, even monolayers from other possible outcomes such as incomplete layers, and beyond the elastic limit. Fundamentally, this mechanical behavior is multilayer, which offers future guidance of CVD experiments. Ideally the hypothesized to be a result of a back-stress that develops in the confined Al design rules can be connected to fundamental processes of growth, but the core during compression loading that causes nucleated dislocations to data sparsity and missing critical information did not allow us to take this retrace their paths or otherwise annihilate during unloading. In this study, path. The presentation will focus on the challenges of constructing a molecular dynamics simulations are utilized to investigate the role that suitable database, the statistical challenges incurred due to its relatively geometry and material properties play on the unique mechanical behavior limited size, and offers a view into the wealth of information which can be of CSNs, with special attention paid to the roles of the core material and accessible from a combination of experiment and ML in advancing complex core-shell interface structure, along with supporting stress calculations. growth processes. An important conclusions remains a call to experimentalists to report failed experiments, which are an important B5-11 Tribocorrosion Behaviors in Seawater of TiSiCN Coatings Deposited aspect in building an informative map of the multidimensional growth by High Power Impulse Magnetron Sputtering: In-situ Electrochemical parameter space. [1] A. Costine, P. Delsa, T. Li, P. Reinke, P.V. Response, Yixiang Ou ([email protected]), Beijing Radiation Center, Balachandran, J. Appl. Phys. 128 235303 (2020) China; H. Wang, Beijing Normal University, China; J. Luo, Beijing Radiation Center, China; B. Liao, X. Zhang, Beijing Normal University, China; W. B6-2 Kinetic Monte Carlo Simulations of Residual Stress Evolution, Eric Wang, Beijing Radiation Center, China; X. Ouyang, Northwest Nuclear Chason ([email protected]), A. Bower, Brown University, USA Technology Institute Kinetic Monte Carlo (KMC) simulations have been a useful way to model To meet the requirement and needs of seawater lubrication for mechanical the evolution of surface morphology during thin film growth. However, it components in marine industry, nanostructured coatings with has been difficult to include stress in KMC simulations because of the long simultaneously high hardness and toughness are expected to deposit on range nature of stress fields. In this work, we have used an approximation component surface to enhance working performance and lifetime. Hence, that focuses on the stress development at the grain boundaries that allows in this work, TiSiCN nanocomposite coatings were deposited on Si (100) us to overcome this problem. The results enable us to investigate how and AISI 316L stainless steel wafers by high power impulse magnetron residual stress depends on the growth conditions (growth rate, sputtering (HiPIMS) at various peak power of 4-8 kW and negative temperature, particle energy) and microstructure (grain size) during thin substrate bias of 0- -200V. Metal Ti and MAX phase Ti3SiC2 layers serve as film growth. . In particular, the KMC shows how the flux of deposited atoms adhesion and transition layers, respectively. Nanocrystalline (nc)- on the surface leads to a supersaturation that creates compressive stress in 2 (TiN,TiC,TiCN)/amorphous (a)-(Si3N4, SiC, sp -C) nanocomposite structure is the film. obtained in TiSiCN nanocomposite coatings, which exhibits high surface/interface integrity and dense microstructure without distinctly B6-3 Maximum N Content in a-CNx and other Amorphous Nitrides, Jiri Houska ([email protected]), University of West Bohemia, Czech Republic preferred orientation. At 7 kW and -60 V, TiSiCN/ Ti3SiC2/Ti coatings with high H, H/E*, H3/E*2 and adhesion exhibit high open circuit potential of - Structures of amorphous CNx materials are predicted by extensive ab-initio 0.07 V, low COF of 0.25 and specific wear rate of 6.1×10-7mm3N-1m-1, molecular-dynamics simulations (more than 800 trajectories) in a wide resulting from mild abrasive wear without the occurrence of pitting range of compositions and densities [1]. The predicted lowest-energy corrosion in 3.5 wt.% NaCl aqueous solution. Moreover, cycling densities are in agreement with the experiment. The main attention is paid tribocorrosion tests exhibit that passive films possess strong abilities of to the formation of N2 molecules, with the aim to predict and explain the regeneration and repairation on sliding contact surface thanks to high maximum N content in stable CNx networks. The results show that the surface/interface integrity and dense microstructure. maximum N content is of »42 at.%. From the kinetics point of view, higher N contents lead to steeply increasing rate of N2 formation during materials formation. The preferred structures may contain some unbonded N2 Hard Coatings and Vapor Deposition Technologies molecules at N contents above »34%, and that they contain many unbonded N2 molecules at N contents above »42%. From the Room On Demand - Session B6 thermodynamics point of view, networks with more than »42% of N Interplay Between Computational and Experimental bonded in them may be temporarily stabilized by N2 molecules sitting in voids around the network, but a subsequent N2 diffusion into the Design of Coatings and Processes I atmosphere makes them unstable. Next, the methodology is applied to B6-1 Data-driven Assessment of Chemical Vapor Deposition of MoS2: a other amorphous nitrides such as Si-C-N [2]. Increasing Si/C ratio from 0 to Meta-Study Based on Published Growth Experiments, A. Costine, 100% leads to increasing maximum achievable content of bonded N: from University of Virginia, USA; P. Delsa, Lousiana School for Math, Science, and 34% to 57% in the case of no N2 formation and from 42% to 57% when the the Arts, USA; T. Li, Petra Reinke ([email protected]), P. Balachandran, amorphous network forms in parallel to N2 formation. The evolution of University of Virginia, USA experimentally achieved N contens in Si-C-N films prepared by reactive Transition metal dichalcogenides (TMD) are highly coveted materials with magnetron sputtering is in an excellent agreement with the prediction. unique properties. The growth of high quality two-dimensional TMD Further analysis shows that while the N2 formation at a given total N monolayers is critical for enabling key technological solutions. Proof-of- content and in a wide range of Si/C ratios is given only by the packing concept devices can be assembled using micromechanical exfoliation from factor, the lowest-energy packing factor increases with Si/C. The results are multilayer material, but this is a prohibitively slow process. Another important for the design of amorphous nitrides for various technological challenge remains the control and minimize defects including point defects applications, prediction of their stability, design of pathways for their and grain boundaries, which have an outsized impact on electronic preparation, and identification of what may or may not be achieved in this properties. It is therefore necessary to understand the complex parameter field. space of TMD monolayer growth, and then adapt, and extrapolate to [1] J. Houska, Acta Mater. 174, 189-194 (2019) conditions suitable for materials integration. For this purpose we asked a [2] J. Houska, ACS Appl. Mater. Inter. 12, 41666-41673 (2020) deceptively simple question: how much can we learn from the published data on MoS2 growth with chemical vapor deposition from solid precursors B6-4 Transition Metal Carbonitride based Thin Films: A Critical Review on (MoO3 and S)? Can machine learning predict the processing conditions Thermal and Elastic Properties of Group IV to VI TMC1-xNx, T. Glechner, TU resulting in single layer MoS2 ? [1] This work consists of two parts, which Wien, CDL-SEC, Austria; P. Mayrhofer, TU Wien, Austria; S. Kodambaka, are equally important, and combine experimental and computational University of California Los Angeles, USA; R. Hahn, TU Wien, CDL-SEC, expertise: firstly, the data mining of the literature, assessment of the Austria; D. Holec, Montanuniversität Leoben, Austria; T. Wojcik, TU Wien, experimental descriptions, and isolation of suitable and reliable parameters Institute of Materials Science and Technology, Austria; M. Arndt, Oerlikon which can be entered into ML algorithms, and secondly, testing and Balzers, Oerlikon Surface Solutions AG, Liechtenstein; S. Kolozsvári, Plansee identification of suitable ML approaches. This is a non-trivial problem Composite Materials GmbH, Germany; Helmut Riedl because the processing space is vast and lack of a priori guidelines impedes ([email protected]), TU Wien, CDL-SEC, Austria rapid progress. Starting from the literature data on MoS2 thin films a Cubic transition metal (TM) carbides and nitrides are well established in database is manually constructed from 82 publications. Unsupervised and various industrial applications especially as thin films due to their refractory supervised machine learning methods are used to learn from the compiled character including highest thermal stability, chemical inertness, as well as data by extracting trends that underlie the formation of MoS2 monolayers. high hardness. Based on their bonding characteristics – dominated by

On Demand available April 26 - June 30, 2021 14 On Demand available April 26 - June 30, 2021 mixtures of strong ionic, covalent, and metallic bonds between their metal B6-7 Superlattice Design for Superior Thin Films, Nikola Koutná and carbon/nitrogen atoms – these compounds are strongly limited with ([email protected])1, R. Hahn, J. Buchinger, TU Wien, Institute respect to ductility compared to metals and metallic alloys. Therefore, to of Materials Science and Technology, Austria; D. Sangiovanni, Linköping overcome these limitations as well as further weak points, e.g. oxidation University, Sweden; M. Bartosik, TU Wien, Institute of Materials Science resistance or electrical properties, the formation of carbonitrides by and Technology, Austria; D. Holec, Montanuniversität Leoben, Austria; P. substitutional alloying of non-metal sites is an interesting approach. Recent Mayrhofer, TU Wien, Institute of Materials Science and Technology, Austria studies in the field of TM carbonitrides highlighted promising candidates as Superlattice architecture—comprising coherently grown nanolayers of two well as selection criteria [1,2]. Here the valence electron concentration or more materials—provides a vast playground for tuning physical (VEC) as well as structural defects such as point or Schottky defects play a properties of thin films via altering different phases and their mutual prominent role. orientation, the bilayer period, or the defect content and distribution close Within this study, we therefore compared the thermal and elastic to interfaces. Changes in these parameters can induce remarkable effects, properties of selected carbonitride based coating materials of the group IV such as partial structural transformations, superhardening and/or to VI (e.g. Hf-C-N or Ta-C-N) transition metals utilizing theoretical and supertoughening. Nevertheless, identifying the layer materials, optimising experimental methods. Various coating materials, also including the binary the film deposition setup and performing micromechanical testing requires base systems, have been deposited by reactive and non-reactive delicate experimental work. This talk illustrates the necessary interplay magnetron sputtering techniques and subsequently characterized with between modelling and experimental techniques to understand and respect to structure, morphology, chemical composition, and mechanical control bilayer-period-dependent trends coming hand in hand with characteristics – also including micro mechanical testing. These results have microstructural changes in superlattices. The model superlattice systems been correlated with ab initio calculations utilizing the Vienna Ab Initio are cubic-based MoN/TaN, TiN/WN, and TiN/TaN. In particular, we Simulation Package. The obtained results clearly indicated that the highlight the important role of vacancies triggering local changes in the synthesis of single phase structured fcc TMC1-xNx structures gets more electronic structure, stabilisation of (novel) metastable phases or challenging from group IV to VI. Nevertheless, the enhancement of the compositional variations at different layer thicknesses, which directly fracture toughness through non-metallic alloying is an appropriate influence mechanical properties. Furthermore, atomistic processes 1/2 approach – e.g. an increase for KIC from 1.8 to 2.9 MPam for TaC0.81 governing strength, plasticity, and fracture of superlattices subject to compared to Ta0.47C0.34N0.19 [2]. In addition, thermal treatments suggest an tensile and shear deformation are discussed in light of the experimental enhancement of the hot hardness and oxidation resistance with deductions results as well as ab initio molecular dynamics simulations. on the still high phase stability. In summary, TMC1-xNx coatings depict an interesting alternative to other thin film materials but still require a more detailed scientific exploration. Hard Coatings and Vapor Deposition Technologies References Room On Demand - Session B7 [1] K. Balasubramanian, et al., Valence electron concentration as an Plasma Surface Interactions, Diagnostics and Growth indicator for mechanical properties in rocksalt structure nitrides, carbides Processes and carbonitrides, Acta Mater. 152 (2018) 175–185. [2] T. Glechner, et al., Assessment of ductile character in superhard Ta-C-N B7-1 INVITED TALK: Energy and Momentum Fluxes at Plasma Processing thin films, Acta Mater. 179 (2019) 17–25. of Materials, Holger Kersten ([email protected]), T. Trottenberg, M. Klette, L. Hansen, A. Spethmann, F. Schlichting, IEAP, U Kiel, Germany B6-5 INVITED TALK: Weakest Links in Superlattices: Insights from Ab Initio INVITED Modelling, David Holec ([email protected]), Montanuniversität For an optimization of plasma-based processes as thin film deposition or Leoben, Austria; N. Koutná, TU Wien, Austria; L. Löfler, L. Hantzenbichler, surface modification, respectively, suitable diagnostics are required. In Montanuniversität Leoben, Austria; P. Řehák, Central European Institute of addition to well-established plasma diagnostic methods (e.g. optical Technology (CEITEC), Brno University of Technology, Czech Republic; M. emission spectroscopy, mass spectrometry, Langmuir probes, etc.) we Bartosik, TU Wien, Austria; M. Friák, Institute of Physics, Academy of perform examples of “non-conventional” low-cost diagnostics, which are Sciences of the Czech Republic, Czech Republic; M. Černý, Central European applicable in technological plasma processes. Examples are the Institute of Technology (CEITEC), Brno University of Technology, Czech determination of energy fluxes by calorimetric probes and measurement of Republic; P. Mayrhofer, TU Wien, Institute of Materials Science and momentum transfer due to sputtered particles by force probes. In Technology, Austria INVITED particular, energy and momentum transfer transport through the plasma Superlattice design has been shown effective to improve Young's modulus, sheath combined with the possibility to measure the effect of charge hardness and toughness of many nitride systems beyond the performance carriers as well as energetic neutrals are of interest and become possible of individual building blocks, especially when the bi-layer period is very by these diagnostics. small, in nm range. Such developments are crucial in order to reach the Total energy fluxes from plasma to substrate have been measured by ever-increasing demands on the coatings (often based on nitrides, carbides special calorimetric sensors. A typical method is the passive thermal probe or oxides) protecting various working tools. While a structural (PTP) based on the determination of the temporal slope of the substrate heterogeneity---as interfaces---serves as an obstacle for dislocation motion, surface temperature (heating, cooling) in the course of the plasma process. it could also act as a sink for impurities or other point defects with a By knowing the calibrated heat capacity of the sensor, the difference of the possibly detrimental effect on interface strength. And even if one thinks time derivatives yields the integral energy influx to the surface. about an ideal interface, chemical inhomogeneity certainly influences local Simultaneously, the electrical current to the substrate can be obtained and electronic structure and hence bonding, which could lead to weakened by variation of bias voltage the energetic contributions of charge carriers bonding. can be determined. By comparison with model assumptions on the This contribution deals with a principal question whether interfaces are the involved plasma-surface mechanisms the different energetic contributions weakest link in the superlattices. We will present examples of calculated to the total energy influx can be separated. tensile strength of various cubic nitride systems (TiN/CrN, TiN/AlN, AlN/VN, Furthermore, for thin film deposition by sputtering it is essential to MoN/TaN...) and discuss the local strength together with details of the determine the sputtering yield as well as the angular distribution of local atomic structure. A large set of systems (with different lattice sputtered atoms. In addition to simulations (TRIM, TRIDYN etc.) an mismatch, stability, magnetic state, etc.) we have treated in the past will experimental determination of the related quantities is highly demanded. serve as a basis for drawing general conclusions (e.g., can strength be For this purpose, we developed a suitable interferometric force probe. The locally enhanced by modifying interatomic distances?). In addition, we will sensitive probe bends a few µm due to momentum transfer by the compare these trends with those predicted for a purely metallic Ti/Ta bombarding and released particles, i.e. sputtered target atoms and recoiled superlattices as well as cubic/wurtzite TiN/AlN multilayers. ions. By knowing the material properties of the cantilever and by measuring its deflection, the transferred momentum, e.g. the force in µN range, can be determined experimentally. In the present study,

1 2020 Student Award Finalist On Demand available April 26 - June 30, 2021 15 On Demand available April 26 - June 30, 2021 measurements are compared with TRIM simulations for different and scanning electron microscopy indicates the formation of a surface layer experimental discharge conditions. with similar phase composition for intermetallic and their corresponding composite cathode types. The average arc voltages do not follow the trend B7-3 A Force Probe as a Tool to obtain Directionally Resolved Momentum of cohesive energies of Nb, Al and intermetallic Nb–Al phases, which have Characteristics during Sputter Processes, Mathis Klette been calculated using density functional theory. Possible reasons for this ([email protected]), T. Trottenberg, M. Maas, H. Kersten, Kiel effect will be discussed based on the current knowledge of multi-element University, Kiel, Germany arc cathodes and their arc plasma available in literature. Ion beam sputter deposition is a well-established technique for producing high quality thin film coatings. The optimization of the coating process B7-5 Oxygen Diffusion Barrier On Interfacial Layer Formed With Remote requires an understanding of the physical phenomena. Process parameters Nh3 Plasma Treatment, Fu-Yang Chu ([email protected]), K. Chang- like the deposition rate can be determined by quartz crystal microbalances, Liao, D. Ruan, H. Yeh, S. Yi, Y. Chien, National Tsing Hua University, Taiwan while charged particles in the sputter plume can be characterized by In this work, the effects about an additional post interfacial layer (IL) Faraday cups or retarding field analyzers. plasma treatment for germanium (Ge) n-type metal oxide semiconductor However, the majority of the sputter plume consists of neutral particles. field effect transistor (nMOSFET) has been discussed in detail. It is founded Characterizing these requires much more complex diagnostics, such as that the electrical performance could be further improved by an additional optical emission, laser-induced fluorescence [1], or mass spectrometry [2]. plasma treatment after the traditional germanium dioxide IL formation. The Ge nMOSFET with NH3 plasma treatment exhibits higher on-off current In contrast, interferometric force probes offer a more direct measurement ratio, lower subthreshold swing and higher Gm value, while the equivalent of all particles including neutrals by measuring the force the sputter plume oxide thickness or gate dielectric quality might be kept. exerts onto the probe surface. In previous works, these probes have been used to determine the thrust of electric space propulsion engines, forces exerted by a low-temperature plasma onto a solid boundary [3], or the recoil of reflected and sputtered particles at a sputter target [4]. Hard Coatings and Vapor Deposition Technologies In this work, a sputter plume is generated by an ion beam directed onto a Room On Demand - Session B8 rotatable copper or silver target, respectively. In order to obtain a HiPIMS, Pulsed Plasmas and Energetic Deposition directionally resolved momentum profile, a force probe is circling the target at a fixed distance, measuring the current and momentum B8-1 INVITED TALK: Evolution of Ionization Fraction of Sputtered Species transferred to the probe surface. The obtained momentum profiles are in Standard, Multi-pulse and Reactive HiPIMS, M. Fekete, K. Bernatova, P. then compared with numerical simulations using SRIM [5]. Both, Klein, J. Hnilica, Petr Vasina ([email protected]), Masaryk University, measurements and simulations, are carried out for different angles of Brno, Czech Republic INVITED incidence, ion energies, gases, target materials, and working pressures. High power impulse magnetron sputtering (HiPIMS) technology attracts the References interest of the industry as the coatings deposited by HiPIMS exhibit enhanced properties compared to conventional dc magnetron sputtered [1] A. Goehlich et al., Nucl. Instrum. Methods,179, 351 (2001) (dcMS) coatings. This is because HiPIMS generates very dense plasma, [2] C. Bundesmann et al., Contrib. Plasma Phys., 55, 737 (2015) which results in a large fraction of ionized sputtered particles. However, a [3] T. Trottenberg und H. Kersten, Plasma Sources Sci. Technol.,26, 055011 significant drawback of HiPIMS is a lower deposition rate compared to (2017) dcMS, which can be mitigated by operation of HiPIMS in multi-pulse mode (m-HiPIMS). M-HiPIMS further changes the coating structure and resulting [4] A. Spethmann et al., Phys. Plasmas, 24, 093501 (2017) properties due to the enhanced ion flux to the substrate because of the [5] J. Biersack und L. Haggmark, Nucl. Instrum. Methods, 174, 257 (1980) interaction of the preceding and the subsequent pulse. The evolution of the sputtered species ionization fraction is studied using a recently B7-4 Erosion and Cathodic Arc Plasma of Nb–Al Cathodes: Composite vs. developed effective branching fraction method. This non-invasive method Intermetallic, S. Zöhrer, M. Golizadeh, Montanuniversität Leoben, Austria; utilizes the optical emission signal to quantify the absolute ground state N. Koutná, TU Wien, Austria; D. Holec, Montanuniversität Leoben, Austria; number densities of the sputtered titanium species. Influence of the A. Anders, Leibniz Institute of Surface Engineering (IOM), Germany; Robert preceding pulse on the subsequent pulse in the non-reactive m-HiPIMS Franz ([email protected]), Montanuniversität Leoben, Austria process is examined as a function of delay between two successive pulses. Cathodic arc deposition has been established as one of the standard techniques for the physical vapour deposition of thin films and coatings as The sputtered species ionization fraction plays an important role also in it allows the synthesis of a wide variety of materials including metallic films, reactive processes. In reactive HiPIMS process, the hysteresis curve is but also nitrides, carbides and oxides if a reactive background gas is used. generally reduced in width and shifted towards lower reactive gas supplies In addition, the highly ionised plasma and the achievable high deposition compared to reactive dcMS. We report on the evolutions of the sputtered rates allow a variety of control mechanisms to influence the film growth species ionization fraction in reactive HiPIMS discharges in oxygen, while the manufacturing costs remain rather low due to the short nitrogen and acetylene gases for a constant mean power and pulse deposition times. With the advent of multifunctional thin films and duration, when varying the repetition frequency. The ionization fraction of coatings, the use of multi-element cathodes providing the non-gaseous the sputtered species increases with the partial pressure of the reactive elements during the synthesis has become an industrial standard. gas, which was attributed to a combination of different effects taking place However, a detailed understanding of the discharge properties is vital for in HiPIMS plasma. Further, the hysteresis curve shape changes with the the further optimisation of the deposition processes to enable synthesising change of the repetition frequency. Larger ionization fraction of the thin films or coatings with improved properties. sputtered species leads to larger difference in the hysteresis curve shape. The hysteresis behavior of reactive HiPIMS is modelled utilizing a modified In the case of single-element cathodes, many properties of cathodic arcs Berg model. The back-attraction of the sputtered species to the target is show a correlation to the cohesive energy of the cathode material including incorporated into the modified Berg model. The results from simulations the burning voltage, the erosion rate, or, to a lesser extent, plasma prove that the back-attraction of sputtered metal ions is the main effect properties like electron temperatures or average ion energy and charge causing the hysteresis curve reduction and shift in reactive HiPIMS states. For multi-element cathodes, various phases with different cohesive compared to reactive dcMS. energies can initially be present in the cathode, or form due to arc exposure, complicating the evaluation of such correlations. To test the B8-3 Dynamics of the Titanium Ground State Atoms and Ions in HiPIMS influence of morphology and phase composition of multi-element cathodes Discharge, Jaroslav Hnilica ([email protected]), P. Klein, P. Vasina, on cathodic arc properties, we used a Nb–Al cathode model system that Masaryk University, Brno, Czech Republic; R. Snyders, N. Britun, University includes: pure Nb and Al cathodes; intermetallic Nb3Al, Nb2Al and NbAl3 of Mons, Belgium cathodes; and 3 composite Nb–Al cathodes with atomic ratios High power impulse magnetron sputtering (HiPIMS) is a very attractive corresponding to the stoichiometric ratios of the intermetallic phases. physical vapor deposition technique, which has been of great interest over Pulsed cathodic arc plasmas from these cathodes were examined using a the last two decades. Continuous development of the HiPIMS-based mass-per-charge and energy-per-charge analyser, showing that charge- sputtering discharges is tightly related to the more profound understanding state-resolved ion energy distributions of plasmas from the intermetallic of the undergoing physical processes, a crucial factor for the optimization and corresponding composite cathodes are nearly identical. An of thin-film growth as well as for further development of sputtering examination of converted layers of eroded cathodes using x-ray diffraction technology in general. On Demand available April 26 - June 30, 2021 16 On Demand available April 26 - June 30, 2021 In our study, we combined various optical diagnostic methods for in-situ B8-5 Understanding and Influencing the Energy Delivered to the Film in characterization of HiPIMS discharges. Special attention was dedicated to Bipolar HiPIMS, Tomas Kozak ([email protected]), A. Pajdarova, J. Capek, the visualization of the ground state titanium neutrals and ions in the University of West Bohemia, Czech Republic; M. Cada, Z. Hubicka, Institute discharge volume as their direct imaging above the magnetron target is a of Physics, Academy of Sciences of the Czech Republic; P. Mares, HVM straightforward way to obtain information about their number density. Plasma, s.r.o., Czech Republic Two-dimensional time-resolved density mapping of the sputtered particles Benefiting from high degree of ionization of process gas and, especially, in a HiPIMS discharge was performed by laser-induced fluorescence (LIF) target material atoms, the high-power impulse magnetron sputtering technique. Atomic absorption spectroscopy (AAS) measurements were (HiPIMS) technique provides increased energy delivered to the film utilized in parallel to LIF to follow the number density evolution of resulting in hard, dense and defect-free coatings [1]. Asymmetric bipolar sputtered species. Above mentioned methods were used to study effects pulsed magnetron sputtering is one of the major techniques used for such as plasma-on time, plasma-off time, gas pressure, pulse energy, or deposition of dielectric films allowing the neutralization of charge on the oxygen addition on density evolution of sputtered particles. target during a positive voltage pulse on the magnetron. Moreover, the As a result of discharge characterization, the number densities, as well as positive magnetron voltage causes an increase of plasma potential leading temporal propagation of the neutral and ionized sputtered titanium atoms to enhanced energies of ions incident on the growing film [2]. Using the were determined. The result shows that atoms always remain in the positive pulse in a HiPIMS discharge, where the degree of ionization is discharge volume, the plasma-off time duration mainly alters the amount much higher, can result in substantial increase of energy delivered to the of background sputtered atom densities at which the successive pulse film and improvement of film properties [3]. Additionally, this technique starts. At the same time, the plasma pulse duration together with the pulse might be more suitable for the industry than using separate substrate bias energy, significantly affect ionization degree of the sputtered titanium source. above the magnetron cathode, especially shortly after the HiPIMS pulse. This paper presents a systematic study of ion energy spectra in a bipolar On the other hand, the observed titanium atom and ion density dynamics HiPIMS discharge employing a rectangular positive voltage pulse (with are weakly sensitive to the plasma pulse duration which implies that the controllable amplitude, delay after the main negative pulse and pulse initial stages of HiPIMS pulse have a stronger influence on the sputtering length). The time-averaged spectra of ions measured at the substrate process evolution. position exhibit a prominent high-energy peak corresponding to the ions The results obtained in this study can be utilized to control the ionization accelerated by the increased plasma potential during the positive pulse. degree, sputtering rate, as well as the other discharge parameters in The position of the peak can be varied by positive pulse amplitude, its size industrial deposition processes involving HiPIMS discharges. scales with the pulse length and its width can be slightly influenced by the delay of the positive pulse. Moreover, time-resolved mass spectroscopy B8-4 The Single-Shot Spatial-Resolved OES of the Spoke in Non-Reactive has been used to analyze the time of arrival of ions at various energies. HiPIMS, Marta Šlapanská ([email protected]), M. Kroker, J. Features of the energy spectra related to the magnetron voltage transients Hnilica, P. Klein, P. Vašina, Masaryk University, Czechia were identified. They indicate changes of the plasma potential in front of The rotating plasma patterns, also known as ionisation zones or spokes, the substrate. To fully understand the ion energy spectra, the mass firstly observed in non-reactive high power impulse magnetron sputtering spectroscopy results are supported by Langmuir probe measurements of discharges (HiPIMS) are at certain conditions present in direct current plasma and floating potential, and also electron density and temperature, magnetron sputtering (dcMS) and radio frequency magnetron sputtering at several positions in the discharge. discharges (rfMS) as well. The spokes are investigated due to their high References impact on the deposition process and sputtered species' transport. To better understand the spoke phenomena, it is necessary to acquire [1] Sarakinos K, Alami J and Konstantinidis S, Surf. Coat. Technol.204 (2010) comprehensive data of the plasma parameters inside the spoke; however, 1661 in HiPIMS, preferably by non-invasive diagnostics. [2] Bradley J W and Welzel T J. Phys. D: Appl. Phys.42 (2009) 093001 This contribution presents the non-invasive spatial-resolved optical [3] Santiago J A, Fernández-Martínez I, Kozák T, Capek J, Wennberg A, emission spectroscopy (OES) of the plasma inside the spoke conducted in Molina-Aldareguia J M, Bellido-González V, González-Arrabal R and non-reactive HiPIMS discharge. The pulses have a duration of 100 µs with a Monclús M A Surf. Coat. Technol. (2019) 358 43 repetition rate of 5 Hz. The 3-inch titanium target was utilised. The experiment was run at argon pressures of 0.4 Pa, 1.0 Pa, and 1.6 Pa to B8-6 The Use of HiPIMS with Positive Pulses to Tailor Film Ion Assistance investigate both triangular and round spokes. and the Resulting Microstructural Properties, Ivan Fernandez ([email protected]), J. Santiago, A. Wennberg, A. Mendez, The fast photodiode and the cylindrical probe were used to capture and Nano4Energy SL, Spain; F. Papa, GP Plasma, USA determine the passing spoke position. The photodiode's signal and the Recently, it has been demonstrated that the addition of a positive voltage probe signal were synchronised with the optical emission spectrum pulse adjacent to the negative HIPIMS sputtering pulse allows the increase acquisition by the intensified charge-coupled device (ICCD) detector with a of film ion assistance and thus, the improvement of coating properties on gate time of 100 ns. By processing these three signals and creating the both biased and insulating substrates. Also, the energy of the incoming ions normalised time scale for each spoke, the unified spoke (UNI-spoke) has is proportional to the amplitude of the positive voltage. Some examples of been created. Consequently, the evolutions of the selected emission lines experiments carried out in industrial coating machines will be presented in can be shown within the UNI-spoke. this study, such as the improvement on film density, mechanical properties The spatially resolved emissions of Ar atom and ions and Ti atoms and ions and deposition rate in an industrial batch coater for metal nitrides, or the spectral lines were investigated within the UNI-spoke. The spatial resolved increased barrier performance of films deposited on PET in an industrial OES measurements have shown that the Ar and Ti atoms and ions spectral scale (330 mm wide web) web coater. lines have the characteristic evolution of a specific species' intensity and is L. Velicu et al., Surface & Coatings Technology 359 (2019) 97. the same for all observed spectral lines of this species within the spoke independently of applied pressure. The Boltzmann plot method was J. Keraudy et al., Surface & Coatings Technology 359 (2019) 433. utilised to determine the excitation temperatures within the UNI-spoke. N. Britun et al., Appl. Phys. Lett. 112 (2018) 234103. The excitation temperatures obtained using the Ar ions and Ti atoms and F. Avino et al., Plasma Sources Sci. Technol. 28 (2019) 01LT03. ions are 13000 K, 8000 K, and 19000 K. The ionisation fraction has been calculated from the selected spectral lines of titanium atom and ion. The J.A.Santiago, I Fernandez-Martinez et al., Surface & Coatings Technology ionisation fraction reaches approximately 40%, and its evolution and 358 (2019) 43. excitation temperature evolutions remain constant in the margin of B.Wu et al., Vacuum 150 (2018) 216. standard error within the UNI-spoke for all investigated working pressures. G. Eichenhofer, I Fernandez-Martinez et al., UJPA 11(3), (2017) 73 This research was supported by project LM2018097 funded by the Ministry B8-7 Measurements and Modeling of Residual Stress in Sputtered Nitride of Education, Youth and Sports of the Czech Republic and project GA19- Films: Dependence on Growth Rate and Gas Pressure, Zhaoxia Rao 00579S funded by the Czech Science Foundation. ([email protected]), E. Chason, Brown University, USA Transition metal nitride films (e.g. TiN, ZrN and TaN) are often used as coatings because of their exceptional physical and mechanical properties. However, the residual stress induced during deposition can significantly On Demand available April 26 - June 30, 2021 17 On Demand available April 26 - June 30, 2021 alter their performance and reliability, leading to failure by cracking or both JMe+ / JG+ and Ji reaching their maximum values. Weakly unbalanced buckling. Therefore, it is of critical importance to understand and control fields with hm = 10 cm provided sufficient flux of activated species to cause the stress evolution during deposition in nitride films. In this work, we the grains to switch to [220] and then to [200] texture and allowing them investigate the stress evolution in nitride coatings deposited by physical to absorb impurities interstitially. This resulted in the elimination of dome- vapor deposition. We report on the dependence of stress on the growth shaped morphology, drastic reduction in roughness, parallel column rate and gas pressure coupled with microstructure characterization. The boundaries and increase in grain size. experimental data is interpreted in terms of a kinetic model which includes Highly unbalanced fields (hm = 4 cm) constricted the height of the the effects of film growth kinetics and energetic processes. The ultimate confinement volume, reducing the ionisation of metal and dissociation of goal is the development of a model for predicting and optimizing stress in nitrogen as evidenced by the significant reduction in JMe+ / JG+. The loss of sputtered nitride films. dissociation switched the texture back to a strong [111]. Grain sizes were B8-9 Wafer-scale Metallic Nanotube Arrays (MeNTAs): Fabrication and significantly larger than for the balanced configuration due to a higher Ji. Application, Alfreda Krisna Altama ([email protected]), J. The hardness and dry sliding wear rates are discussed. Chu, National Taiwan University of Science and Technology, Taiwan; A. Purniawan, S. Wicaksono, Institut Teknologi Sepuluh Nopember, Surabaya, B8-12 On the Influence of the Micropulse on Nb Thin Films Deposited by Indonesia MPPMS and DOMS: A Comparative Study, Y.G. Li ([email protected]), Z. Jiang, H. Yuan, N. Pan, M. Lei, Dalian University of Technology, China Sputter deposition has been widely used in the manufacturing of high- performance on-chip interconnect. The metal connecting lines at each Nb thin films deposited by modulated pulsed power magnetron sputtering layer can be formed by filling trenches and vias in the interlayer dielectrics (MPPMS) and deep oscillation magnetron sputtering (DOMS) were (ILD). High-power impulse magnetron sputtering (HiPIMS) techniques as a comparatively studied under similar average power by controlling the novel ionized physical vapor deposition (IPVD) technology has been micropulse duty cycle. It was found that DOMS discharge showed both developed in view years for metallization in integrated circuits and higher discharge peak current and peak voltage, time delay between the nanostructures manufacturing with high aspect ratio (AR). HiPIMS is an current and voltage was much shorter with respect to a MPPMS discharge. IPVD technique based on pulsed power technology where the peak power All Nb thin films were observed with Nb(110) preferred orientation and exceeds the time-averaged power by roughly two orders of magnitude so. compact columnar structure with DOMS Nb thin films hardness with higher HiPIMS deposition offers a route for depositing uniform coatings onto hardness and elastic modulus. The increase of micropulse duty led to the complex-shaped substrates and structures. In this research, we formed gradually movement of Nb(110) to the high scattering angle direction, high AR trenches using photoresist lithography on silica wafers. The meanwhile the DOMS Nb(100) diffraction peaks were all on the left of deposition process was performed using a 6 inch diameter metallic alloy MPPMS Nb(110). An anomalous increase could be observed for target using HiPIMS and DCMS. The plasma properties were measured compressive residual stress s of Nb thin films for both techniques. The using a Langmuir probe at a distance of 70 mm from the target face and anomalous increase in s also led to the deterioration of scratch adhesion. below the racetrack. The measurement results show that the plasma Despite, the grain sizes of DOMS Nb thin films were all smaller than produced by HiPIMS has a higher ion and electron density value compared MPPMS Nb thin films, s in DOMS Nb thin films generated by the adatom to DC plasma. We consider the experimental condition of high density diffusion and ion irradiation still overwhelmed the tensile stress generated plasma as the favorable process condition for the trench deposition. In this by the volume shrinkage of the growing grains. The special afterglow of condition, the film was deposited at different power and working pressure. DOMS in microsecond time scale gave a new dimension controlling the The cross-sectional pictures performed by scanning electron microscopy grown thin films. (SEM) shows that the film had good trench step coverage and amorphous B8-13 The Effect of Metal Transition Dopents on Mechanical Properties structure. Furthermore, the results of this study can be used as a reference TiBCN Based Coatings Deposited by CFUBMS-HiPIMS, Ihsan Efeoglu for trench filling and the manufacture of nanostructures with high aspect ([email protected]), Ataturk University, Turkey; N. Aksakalli, Atatürk ratio using HiPIMS. University, Turkey; B. Gumus, E. Tan, Aselsan Inc., Turkey B8-10 Plasma Chemistry, Crystal Growth and Mechanical Properties of Ternary and quaternary hard coatings based on carbonitrides of transition CrAlYN / CrN Nanoscale Multilayer Coatings Deposited by High Power metals with amorphous matrix have many advantages; these have high Impulse Magnetron Sputtering, Arutiun Ehiasarian hardness, adhesion, abrasion, oxidation, and corrosion resistance. ([email protected]), A. Sugumaran, P. Hovsepian, Sheffield Hallam Functional properties can be gained by adding definite amounts of University, UK different transition elements to carbonitride-based coatings. In this study, Nanoscale multilayer coatings based on CrAlYN / CrN find applications in mechanical and tribological properties were investigated by adding Nb and manufacturing, automotive components, power generation turbines and Zr transition elements to TiBCN based coatings. The coatings were petrochemical industry. To perform well in these different environments, deposited on 4140 tool steel and the silicon wafer. TiBCN-based coatings the coating microstructure must be tailored via the deposition process. In with high adhesion and dense microstructure were synthesized with High Power Impulse Magnetron Sputtering (HIPIMS), which provides a high CFUBMS (Pulsed-dc+HiPIMS) using Cr, Ti, TiB2, Nb, Zr targets and Ar, N2, degree of ionisation of the metal flux and activation of the reactive gas, the C2H2 gases. Microstructural properties of the coatings were obtained from relation between process parameters, microstructure and coating the coatings on the silicon wafer and 4140 steel using SEM, XRD, and XPS. properties is not well understood. The mechanical properties of coatings synthesized on 4140 steel base materials have been characterized by Microhardness and Scratch tests. The We report on the effect of unbalancing magnetic field on species- hardness and adhesions of TiBCN-based coatings, which were grown by dependent transport of metal and gas species to the substrate and its adding Nb and Zr, respectively on Cr:CrN graded structure (~200nm) as the influence on film growth, texture formation and mechanical performance transition layer, were optimized depending on the process parameters. of nanoscale multilayer CrAlYN/CrN films. Experiments were carried out in Scratch test results showed that the adhesion strength varied as a function an industrial-sized coater with four cathodes arranged in a closed magnetic of the Nb and Zr target negative bias voltages. The highest adhesion field configuration, two of which were operated in HIPIMS mode and two in strength was obtained as Lc:80N at -800V with adding Zr. In the case of the conventional sputtering. Nb adding, the highest adhesion strength was obtained as Lc:57N. In a balanced configuration, the magnetic null height was hm = 12 cm and Adhesion and microhardness test results showed that the utilization of the volume of plasma near the target was the greatest and resulting in a bias-voltage with HiPIMS to the targets and pulsed-dc to the base material high metal-to-gas ion ratio (JMe+ / JG+) observed by optical emission was the most effective coating parameter in the critical load and the spectroscopy. The transport to the substrate, as measured by the ion hardness properties. Friction coefficients were observed as the lowest saturation current (Ji), was the lowest due to the absence of magnetic field value, µ≈0.163 in TiBCN-Nb coatings, while it was observed as µ≈0.337 in lines connecting to the substrate. The 4-micrometre-thick films exhibited TiBCN-Zr coatings. competitive growth and a strong [111] texture evidenced by XRD due to Keywords: TiBCN:Zr/Nb, Adhesion, Microhardness, CFUBMS-HiPIMS, the relatively low flux of dissociated nitrogen to the surface. SEM observations showed that the [111] texture resulted in dome-shaped column tops and clearly defined column boundaries where vacuum impurities were segregated. As the magnetic field grew more unbalanced, the confinement volume decreased whilst transport to the substrate was enhanced, resulting in On Demand available April 26 - June 30, 2021 18 On Demand available April 26 - June 30, 2021 Hard Coatings and Vapor Deposition Technologies is porous, whereas with Si the oxide is separated into a dense inner region Room On Demand - Session BP and a porous outer region. Therefore, we can conclude that Si-alloying improves the oxidation Hard Coatings and Vapor Deposition Technologies resistance tremendously and may be applicable to increase the (Symposium B) Poster Session performance of other high-entropy nitride coatings in oxidative environments. BP-1 Investigation of Ionized Density Fraction in Reactive Hipims, Katarína Bernátová ([email protected]), Masaryk University, BP-3 Properties of Boron Carbide Thin Films Deposited by Pulsed Laser Czechia Deposition, Falko Jahn ([email protected]), S. Weissmantel, In High Power Impulse Magnetron Sputtering (HiPIMS), high plasma density Laserinstitut Hochschule Mittweida, Germany is achieved by focusing the applied power into the short pulses with a duty Boron carbide is the third hardest known material behind diamond or ta-C cycle of around 2%. Discharge properties, such as a density of sputtered and cubic boron nitride (c-BN). Intensive contact of diamond or ta-C with species, are strongly nonlinearly dependent on the reactive gas supply ferrous materials lead to carbide formation and thus a chemical wear of influencing properties as well as the stoichiometry of the deposited layers. the layer. Because of this, films of diamondlike carbon are not suited for applications e.g. as wear protective layers in steel processing. For cubic In our study, the effect of nitrogen gas admixture on the temporal boron nitride on the other hand there is yet no successful deposition evolution of discharge current, voltage, pressure, and ionized density method that meets industrial requirements. fraction of sputtered species in the HiPIMS process is analyzed. The ionized Boron carbide could be a promising compromise for these applications. density fraction is estimated from the sputtered titanium atom and ion Indeed, it doesn’t reach the hardness values of ta-C or c-BN, but due to its absolute ground state number densities both near the target surface and better thermal and chemical stability it is suitable for ferrous materials. near the substrate region. For the determination of sputtered species density, a well-established spectroscopic method based on effective Using Pulsed Laser Deposition (PLD) super hard coatings of boron carbide branching fractions was utilized. have been produced with a resulting indentation hardness up to 47 GPa which almost reaches the highest values reported so far. The substrate Three regimes within the hysteresis curve were investigated and temperature during deposition has been varied between room compared: metal, transition, and compound regime. In both, target and temperature and more than 500°C. That temperature has been found to substrate regions, after the pulse ignition, the nonzero value of titanium have the most impact on the mechanical properties of the coatings. The atom density is always detected, indicating the presence of residual influence of the ablation fluence on the mechanical properties is shown particles originating from the preceding pulse. Near the target, in the metal although it is less significant. The produced layers show good film regime, the Ti atom density increases through the pulse, causing enhanced adherence properties but a very bad surface quality at layer thicknesses argon rarefaction near the target. From the quarter of the pulse, the sufficient for practical applications and which is characterized by too many concentration of Ti ions is always higher than Ti atoms and the ionized particulates and droplets. density fraction is most pronounced around middle of a pulse. With the Following, research results of applying an alternative boron carbide target nitrogen gas addition, the ionized density fraction increases, despite the are presented. This target is produced by depositing a several ten microns overall Ti atom and ion densities decrease. In the substrate region, the thick boron carbide layer on a steel substrate using PLD. The as deposited evolution of Ti atom and ion densities changes, as the distance from the film is subsequently used as the new target for the deposition process and target is increased, therefore the transport time of particles to the results in boron carbide thin films with a significantly better surface quality. measured area is higher. Furthermore, when operating in the transition Comparing these B4C films to the first deposited ones resulting from and compound regime the pressure increases, resulting in even stronger commonly used targets it can be shown that both number and size of the delay of particle transport. Due to argon rarefaction near the target in the droplets decrease. metal regime, Ti atoms travel towards the substrate where they are BP-4 In-situ Analysis of B-doped Diamond Synthesis using Hot Filament accumulating over the second half of the pulse. In contrast, in the CVD, Ryo Tanaka ([email protected]), M. Takuya, Chiba transition and compound regime, the sputtering is not effective, and the Institute of Technology Graduate School, Japan; Y. Sakamoto, Chiba transport is strongly delayed, therefore the Ti atom and ion densities are Institute of Technology, Japan decreasing through the pulse. Here, the ionized density fraction is again enhanced with nitrogen gas admixture. B-doped diamond (BDD) has excellent electrochemical properties, and its application for electrochemical electrodes is progressing. BDD is prepared in substrates such as Si by hot-filament chemical vapor deposition (HFCVD), BP-2 Increasing Oxidation Resistance of Reactive Magnetron Sputtered microwave plasma CVD, etc. BDD synthesis using HFCVD apparatus, source (AlvCrwNbxTayTiz)N Thin Films by Si-alloying, Andreas Kretschmer gases are decomposed by filaments heated to 2273≦[K] in pressure of ([email protected]), TU Wien, Institute of Materials between molecular flow and viscous flow. Therefore, complicated Science and Technology, Austria; K. Yalamanchili, H. Rudigier, Oerlikon convection occurs between filament-substrate, it’s difficult to control the B Balzers, Oerlikon Surface Solutions AG, Liechtenstein; P. Mayrhofer, TU source flow between filaments and the substrate. In addition to control the Wien, Institute of Materials Science and Technology, Austria flow of gases supplied into the chamber, it is necessary to feedback control High-entropy alloyed nitrides are promising materials for hard coatings. based on measurements of reaction gas states. One major drawback is a lack of oxidation resistance in most coatings, In this study, reaction gas states were measured with quadrupole mass which limits high-temperature applications in ambient conditions. In this spectrometer (QMS) during BDD synthesis, it was explored relationship of work we report a method to increase the oxidation resistance of these electrical resistance to peak intensity of fragments. materials. BDD films were synthesized on Si substrates using HFCVD apparatus. CH4- (AlvCrwNbxTayTiz)N coatings were formed in a cubic (c) solid solution in thin H2-B(OCH3)3 gas mixture was used, with CH4/H2 flow rate: 1/50 [SCCM], film form by reactive magnetron sputtering in N2-atmosphere using a B(OCH3)3 flow rate: 0.025 to 0.150 [SCyCM]. Pressure was 4.0 [kPa]. powder metallurgically prepared metal target (Plansee) with nominal Filament temperature was 2273≦ [K]. Synthesis time was 1 [h]. Reaction composition of 20 at% of each element. Si was alloyed by placing different gas states were measured with QMS. Deposits were evaluated by Raman numbers of pieces (about 2x2x0.4 mm3 each) of Si on the cathode racetrack Spectroscopy. Electrical resistances were measured by four-probe method. during deposition. As a result of measuring reaction gas states with QMS, it was confirmed + + + We measured the oxidation resistance of the coatings by placing the that B(OCH3)3 fragments of (OCH3) , BH(OCH3) and B(OCH3)2 . These peak samples in a furnace in ambient air at 850 °C for 0.5, 1, 5, 10, 30, and 100 h. intensities decreased during synthesis, so, it was recognized that can be After these durations we extracted the samples from the hot zone and measured the B(OCH3)3 with QMS. There was correlation between + analysed them with X-ray diffraction, Energy-Dispersive-X-Ray-Analysis, and decreased electrical resistance and increased peak intensity of (OCH3) up Transmission Electron Microscopy (TEM). After 100 h the oxide scales on to B(OCH3)3 flow rate 0.100 [SCCM]. In the case of B(OCH3)3 flow rate coatings without and with Si were 2800 and 300 nm thick, respectively. exceeded 0.100 [SCCM], electrical resistance indicated constant value. Plotting the oxide scale thickness against the oxidation time reveals a Supersaturated of B and O occurred on the surface of the substrate and parabolic oxide growth behaviour without Si, which changes to logarithmic electrical resistance of CVD diamond became constant value. growth with Si in the solid solution. This different behaviour can be explained with the oxide morphology, visible in TEM. Without Si, the oxide On Demand available April 26 - June 30, 2021 19 On Demand available April 26 - June 30, 2021 In conclusion, it was confirmed that controlling electrical resistance of BDD protective coatings prepared by pulsed magnetron sputtering, Surface and was suggested by in-situ analysis of reaction gas states with QMS. Coatings Technology (2019) 357 364-371 BP-5 Behavior of Partially Oxidized Metal Targets, Jiri Houska [3] S. Debnárová, L. Zábranský, P. Souček, V. Buršíková, P. Vašina, Study of ([email protected]), T. Kozak, University of West Bohemia, Czech W-B-C thin films prepared by magnetron sputtering using a combinatorial Republic approach, International Journal of Refractory Metals and Hard Materials We investigate the oxidation of a wide range of metal surfaces by ab-initio (2019) 85 calculations. The metals of interest span from transition metals (Sc, Y, La, BP-7 Mechanical and Tribological Performance of V-C-N Coatings Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W) through noble and post-transition metals Deposited by RF Magnetron Sputtering, Akram Alhussein (Cu, Ag, Au, Zn, Cd) to the main group (Al) [1,2]. We go through a wide ([email protected]), Universite de Technologie de Troyes (UTT), range (up to 329 per metal) of distributions of O atoms on a partially France; L. Aissani, Khenchela University, Larbi Ben M'Hidi University, oxidized metal surface. First, we focus on the qualitative information Algeria; C. Nouveau, CER Arts et Metiers Paris Tech, France whether the preferred distribution of O atoms is heterogeneous Vanadium nitrides are known as hard and wear resistant materials widely (stoichiometric oxide + metal; e.g. Al or La), homogeneous used for cutting tools and other components. Vanadium carbides present (substoichiometric oxide; e.g. Ti or Zr), homogeneous at low surface oxygen excellent properties at high temperature, such as good wear resistance and coverage and heterogeneous at high surface oxygen coverage (e.g. Sc or Y), high hardness. This work aims to evaluate the influence of the following etc. This is of crucial importance for the quantities such as secondary deposition parameters on the structure, mechanical and tribological electron emission coefficient, which correspond to a weighted average of properties of V-C-N thin films deposited by RF magnetron sputtering: those of stoichiometric oxide and metal only in the case of heterogeneous nitrogen partial pressure, Ar-N2 deposition atmosphere and film thickness. oxygen atom distribution. Second, we correlate these qualitative results VN, V–C-N coatings were deposited on silicon wafers and steel substrates with the known formation enthalpies of oxides of various compositions. and characterized with X-ray diffraction, XPS, EDS, SEM, nanoindentation Third, we provide the quantitative values of adsorption energies and tribological tests. corresponding to the energetically preferred O atom distribution for various partial coverages of various metals by O. We find that the Controlling the gas pressure in the deposition chamber is important to dependence of adsorption energy on the surface oxygen coverage can be elaborate the desirable coatings (good adhesion and performance). It has decreasing (e.g. Al or La), increasing (e.g. Ti or Zr), concave (e.g. Sc or Y), been found that compared to the VN system, the VC-N films showed a etc. These data also include the information about the maximum stable smooth surface and the films deposited at 0.06 Pa presented the best surface oxygen coverage (nonzero but lower than 100% for Cu, Ag, Zn, Cd). mechanical and tribological properties: highest hardness of 26.1 GPa and Fourth, we demonstrate one use of these results by presenting Monte lowest friction coefficient of 0.42 [1]. Carlo simulations of sputtering. Fifth, we utilize the theoretical results in The Variation of nitrogen percentage in the deposition camber (10 - 20%) order to explain the experimental results, such as the time dependence of and the film thickness (0.26 – 2.5 µm) influenced significantly the film the magnetron voltage during sputter cleaning of oxidized metal targets structure, hardness and wear resistance. Multiple phases of V2N and VN (monotonic e.g. for Al but non-monotonic e.g. for Ti). were formed and the thick films containing more nitrogen were slightly [1] J. Houska and T. Kozak, J. Appl. Phys. 121, 225303 (2017) dense compared to the thinner ones [2]. [2] J. Houska and T. Kozak, Surf. Coat. Technol. 392, 125685 (2020) Keywords: Vanadium carbonitride thin films, PVD, microstructure, mechanical properties, tribological performance. BP-6 Phase Formation, Thermal Stability and Mechanical Properties of References: Nb-B-C Thin Films Prepared by Magnetron Sputtering Using a Combinatorial Approach, Stanislava Debnarova ([email protected]), [1] Linda Aissani, Akram Alhussein, Corinne Nouveau, Lamia Radjehi, Issam P. Soucek, V. Bursikova, Masaryk University, Czechia; S. Mraz, M. Hans, J. Lakdhar, Elia Zghei, Evolution of microstructure, mechanical and Schneider, D. Holzapfel, RWTH Aachen University, Germany; P. Vasina, tribological properties of vanadium carbonitride coatings sputtered at Masaryk University, Czechia different nitrogen partial pressures, Surf. Coat. Tech. 374 (2019) pp. 531- 540. The performance and lifetime of a tool can be significantly improved by the use of an appropriate protective coating. The most commonly used [2] Linda Aissani, Akram Alhussein, Corinne Nouveau, Laala Ghelani, materials for these applications are ceramic-based coatings, favoured due Mourad Zaabat, Influence of film thickness and Ar-N2 plasma gas on the to their high hardness. However, these coatings are inherently brittle which structure and performance of sputtered vanadium nitride coatings, Surf. enables the spreading of cracks and coating failure. Therefore, new Coat. Tech. 378 (2019) 124948. materials are being explored, which would combine the hardness of BP-8 Radiation Stability of nc- ZrN/a-ZrCu Multilayered Films after He ceramics with a degree of ductility. Implantation, Grégory Abadias ([email protected]), Ab-initio calculations have predicted that such a combination of properties Institut Pprime - CNRS - ENSMA - Université de Poitiers, France; V. Uglov, S. could be present in a crystalline X2BC material where X is a transition metal Zlotski, I. Saladukhin, Belarusian State University, Belarus such as Mo, Ti, V, Zr, Nb, Hf, Ta or W [1]. Out of this group, only crystalline The development of a new generation of nuclear reactors requires the use Mo2BC has been successfully prepared and studied so far. There have been of materials and coatings with high radiation resistance. It’s necessary to attempts to prepare a W2BC phase but these remain unsuccessful due to create materials with a large number of sinks for point defects, such as the near-zeroenthalpy of formation of this material. However, these dislocations, grain boundaries, and interphase boundaries to achieve this studies have shown that the X-B-C system exhibits interesting mechanical goal [1-2]. One of the most promising materials with the large number of properties even in an amorphous state [2, 3]. grain boundaries are nanocrystalline coatings, for example nc-ZrN, formed This study focuses on the Nb-B-C system as Nb2BC is predicted to have a by vacuum arc deposition [3]. Nanocrystalline coatings with lower enthalpy of formation. The coatings have been prepared by crystalline/amorphous interfaces (such as nanocomposite and multilayered magnetron sputtering from 3 targets using a combinatorial approach. A nc-MeN/a-Si3N4 systems) exhibit a high radiation tolerance along with wide range of compositions has been studied and evaluated in regard to crystalline/crystalline systems, due to amorphous nanolayers associated their structure and mechanical properties. As thermal and oxidation with excellent defects absorption capability [4-5]. In this paper, the idea of stability is a vital requirement for protective coatings, the studied coatings replacing amorphous a-Si3N4 layers with amorphous a-ZrCu metal layers is have been annealed up to 900°C in argon and up to 1000°C in an Ar/O2 gas proposed. mixture. The study examines the effect of annealing on the structure and The work is devoted to the study of the elemental and phase composition, mechanical properties of the coatings. surface morphology and microstructure of the nc-ZrN/a-ZrCu multilayer References systems and their evolution after He implantation. Nanoscale nс-ZrN/a- [1] H. Bolvardi, J. Emmerlich, M. To Baben, D. Music, J. Von Appen, R. ZrCu multilayers with elementary layer thickness of 5 nm/5 nm and 5 Dronskowski, J.M. Schneider, Systematic study on the electronic structure nm/10 nm with different Cu concentration in a-ZrCu layer were grown by and mechanical properties of X2BC (X = Mo, Ti, V, Zr, Nb, Hf, ta and W), J. reactive magnetron sputter-deposition from Zr and Cu targets at substrate Phys. Condens. Matter 25 (4) (2013) 045501 temperature of 300°C. XRD, EDX, SEM and AFM investigation of as- deposited and after He ion irradiation (40 keV and doses up to 1E17 cm-2) [2] S. Debnárová, P. Souček, P. Vašina, L. Zábranský, V. Buršíková, S. of nc-ZrN/a-ZrCu multilayer systems were conducted. Mirzaei, Y. Pei, The tribological properties of short range ordered W-B-C

On Demand available April 26 - June 30, 2021 20 On Demand available April 26 - June 30, 2021 XRD analysis confirms that multilayered films consist of nanocrystalline ZrN films was performed with a UV–vis spectrophotometer. The hardness, and amorphous ZrCu. It was found formation amorphous ZrCu in a wide adhesion and tribological properties of TiOx films were evaluated by range of Cu concentrations (up to 80 at.%). nanoindenter, scratch test and pin-on-disk wear test, respectively. The The influence of the Cu composition (in the range of 20-80 at.%) in the ZrCu corrosion resistance of TiOx films in 0.1 M H2SO4 aqueous solution was layers and thickness of individual layers (5 nm/5 nm and 5 nm/10 nm) of examined by an electrochemical workstation. The influence of target nc-ZrN/a-ZrCu multilayer on radiation stability of elemental and phase poisoning ratios on the deposition rate, microstructure, transmittance, composition, surface morphology (blistering) and microstructure of films hardness, adhesion, wear and corrosion resistance of TiOx films were after He ion irradiation is discussed. studied in this work. [1]. R.W. Grimes et al. Nature Materials 7 (2008) 683. BP-12 The Role of Oxygen Flow Rate on the Structure and Stoichiometry [2]. Xinghang Zhang et al. Prog.Mat. Sc. 96 (2018) 217. of Cobalt Oxide Films Deposited by DC Reactive Sputtering, Nilton Francelosi Azevedo Neto ([email protected]), L. Affonco, São [3]. A.J. Van Vuuren, V.V. Uglov et al. Phys. Status Solidi C 13 (2016) 886. Paulo State University, Brazil; C. Stegemann, D. Marcel Gonçalves Leite , [4]. V.V. Uglov, G. Abadias et al. Sur. Coat. Technol. 344 (2018) 170. Aeronautics Institute of Technology, Brazil; J. Humberto Dias da Silva , São [5]. V.V. Uglov, G. Abadias et al. Nucl. Instr. Meth. Phys. Res. 435 (2018), p. Paulo State University, Brazil 228. The cobalt oxide films were grown on amorphous silica (a-SiO2) in order to investigate the influence of the oxygen gas supply on the stoichiometry, BP-9 Physical and Mechanical Properties of Cr-Al-N and Cr-v-N Ternary structure and orientation texture of polycrystalline cobalt oxide films. The Systems, Ahlam Belgroune ([email protected]), University of films were grown by direct current (DC) reactive magnetron sputtering Technology of Troyes, France; L. Aissani, University of Abbes Laghrour, using a metallic Co target and different oxygen partial pressures by Algeria; A. Alhussein, University of Technology of Troyes, France controlling the inlet flow rate (0.5 to 5.0 sccm) over a dominant argon In the present work, ternary systems (Cr-Al-N and Cr-V-N) thin films were atmosphere (40 sccm) keeping constant the deposition power (80 W) and deposited on steel substrates by magnetron sputtering process. The effect the total working pressure (0.67 Pa). X-ray diffraction results evidence a of Al and V additions on the properties of the binary Cr–N system was strong influence of the oxygen flow over the film’s stoichiometry and evaluated. The morphology and surface topography of the coatings were structure, where low oxygen flows (< 2.0 sccm) favor the formation of the investigated. The hardness and elastic modulus were measured by rocksalt CoO phase, while higher oxygen flows (>2.5 sccm) favor the spinel nanoindentation and the friction coefficient was determined by pin-on-disc Co3O4 phase formation. The coexistence of monoxide and tetraoxide tribometer. phases is observed only for 2.5 sccm oxygen flow condition. Strain and We found that Al addition improved the mechanical properties of the Cr–N orientation texture effects related to the oxygen partial pressure are also system (H= 27 GPa, E= 304 GPa) presenting a dense structure. Contrary, the observed and discussed. Computer simulations indicate that low oxygen V addition deteriorated the mechanical properties of films presenting flow (<2.0 sccm) occur in the metallic regime, while higher oxygen flow rough surfaces (H= 10 GPa, E= 280 GPa). The friction coefficient of the favor the poisoned regime. Consistent with the simulations, cobalt CrAlN films slightly increased with rising Al percentage and varied between emission (CoI = 340.5 nm) from the plasma show a significant decrease 0.42 and 0.61. For the Cr-V-N coatings, the friction coefficient was lower while the oxygen emission (OI = 777.3 nm) is significantly increased when than those obtained for Cr-Al-N and Cr-N films. The wear resistance of Cr- the oxygen flow is increased. Al-N and Cr-V-N coated steel substrates decreased with increasing Al and V BP-13 e-Poster Presentation: Bipolar HiPIMS for Tailoring Ion Energies in contents. Thin Film Deposition, Daniel Lundin ([email protected]), R. Viloan, Keyword: Magnetron sputtering; Cr-Al-N; Cr-V-N; Cr-N; Hardness; Wear. Linköping University, Sweden; M. Zanáška, Linköping University; H. Du, Guizhou University, China; R. Boyd, Linköping University, Sweden; T. BP-10 Understanding Residual Stress in Thin Films: Analyzing the Stress Shimizu, Tokyo Metropolitan University, Japan; U. Helmersson, Linköping Evolution Using a Kinetic Model for Ag, Cu, Ni, Fe, Ti, and Cr, Zhaoxia Rao University, Sweden ([email protected]), S. Berman, Brown University, USA; D. Depla , Ghent University, Belgium; E. Chason , Brown University, USA Bipolar HiPIMS, where a reversed positive pulse is applied to the target following the negative pulse, has promised great potential to solve An analytical model for the evolution of residual stress in polycrystalline challenges in growth of insulating thin films or when insulating substrates thin films is used to analyze numerous previously-reported wafer curvature are used. In this mode of operation, a significant fraction of the ion energy measurements obtained for a variety of processing conditions and distribution functions (IEDFs) can be shifted with an energy proportional to materials (Ag, Cu, Ni, Fe, Ti Cr). The model includes the effects of film the magnitude of the applied reversed potential, Urev⁠ . This is a consequence growth kinetics by considering stress-generating mechanisms at the grain of the fact that a limited region of the plasma, near the cathode, boundary that forms between adjacent grains as well as subsurface grain growth.Non-linear least-squares fitting is used to obtain a set of experiences an increased plasma potential with a value close to Urev⁠ . parameters for each material.Some of the parameters are material- However, the ion energy gain and the distribution of energy in the dependent and are made to be the same for all the data for each material accelerated populations can be affected by the magnetic field independent of the processing conditions; others are allowed to change arrangement, the anode position and shape as well as the HiPIMS pulse with the processing conditions.The dependence of the fitting parameters configuration. These aspects are of great interest in the present on the material and processing conditions is compared with the behavior contribution, where time- and energy-resolved ion mass spectrometry was expected from the physical mechanisms in the model. performed in different discharge configurations to further understand the physics in bipolar HiPIMS discharges. Based on the features of the recorded BP-11 Effect of Target Poisoning Ratios on the Fabrication of TiOX Coatings IEDFs, optimized bipolar HiPIMS deposition processes for relevant material Using Superimposed HiPIMS and MF System, W. Chen, Ming Chi University systems, such as aluminum oxide, were investigated to observe the effect of Technology, Taiwan; B. Lou, Chang Gung University, Taiwan; Jyh-Wei Lee of ion acceleration on the tailoring of the phase constitution during film ([email protected]), Ming Chi University of Technology, Taiwan growth. Titanium oxide film is characterized by its clean surface, sterilization, good BP-14 Nb-C Thin Films Prepared by DC-MS and HiPIMS: Synthesis, abrasion resistance and good corrosion resistance, which make it become a Structure and Tribo-mechanical Properties, Neus Sala functional coating with a wide range of applications.The superimposed high ([email protected]), M. Abad, Institut Químic de Sarrià, Universitat power impulse magnetron sputtering (HiPIMS) and mid-frequency (MF) Ramon Llull, Spain; J. Sánchez-López, Instituto de Ciencia de Materiales de system (superimposed HiPIMS-MF) is a relatively new deposition system, Sevilla, CSIC-Universidad de Sevilla, Spain; J. Caro, Eurecat, Centre which adds MF pulses to the off-time of the HiPIMS for higher deposition Tecnològic de Catalunya, Spain; C. Colominas, Institut Químic de Sarrià, rate.In this study, a superimposed HiPIMS-MF system was used to fabricate Universitat Ramon Llull, Flubetech S.L. , Spain the titanium oxide films. During the deposition process, a plasma emission monitoring (PEM) system was used to feedback control the target Nanostructured Nb-C thin films were prepared by direct current magnetron poisoning ratio of Ti target. Titanium oxide (TiOx) films grown at five sputtering (DC-MS) and via high power impulse magnetron sputtering different target poisoning ratios were deposited on single crystal silicon (HiPIMS). The films have been characterized in depth by XRD, GIXRD, SEM, wafer, glass slide and AISI304 stainless steel plate substrates. The AFM, EPMA and Raman spectroscopy. The mechanical properties have microstructure of thin film was examined by a field emission scanning been measured by means of nanoindentation and the tribological electron microscope. The crystalline structure of thin film was analyzed by properties by pin-on-disk test in ambient air.The wear tracks and the ball an X-ray diffractometry. The optical transmittance measurement of thin scars were analyzed by Raman spectroscopy in order to elucidate the On Demand available April 26 - June 30, 2021 21 On Demand available April 26 - June 30, 2021 tribochemical reactions appearing at the contact and to determine the wear mechanism present in each specimen type. The obtained DC samples were very dense with tunable mechanical and tribological properties depending on the amorphous carbon (a-C:H) content incorporated in the coatings. The crystal and phase composition changed from pure nanocrystalline (formed by Nb2C and NbC phases) to nanocomposite structure (NbC/a-C:H). The samples prepared by HiPIMS developed a marked columnar morphology with a NbC/a-C:H nanocomposite structure. Hardness values range from 11 to 20 GPa depending on the deposition technique and the amount of a-C:H soft phase present in the samples. The tribological properties of all the coatings were remarkably good when the carbon content was around 50 at. %. The formation of alubricant sp2-rich C tribofilm between the ball and the coating during the pin on disk tests was observed by Raman spectroscopy, preferentially in the samples prepared by HiPIMS technique with higher C content. BP-15 Impact of Stacking Sequence with InWZnOx/InWZnOy Bilayer Conductive Bridge Random Access Memory, Chih-Chieh Hsu ([email protected]), P. Liu, K. Gan, D. Ruan, Y. Chiu, National Chiao Tung University, Taiwan; S. Sze, Naitonal Chiao Tung University, Taiwan This work investigates the hybrid oxide devices with different stacking sequence of Cu/TiW/IWZOx/IWZOy/Pt memristor. Typical bipolar resistive switching can be observed in all CBRAM devices. The hybrid oxide device shows good non-volatile memory characteristics, such as endurance cycle, low operation voltage, data retention time and stable on/off ratio. The oxide stacking sequence can improve the endurance cycles to 104, retention time to 104s and more resistance state uniformity. These results have given a prospect for simple and fast method to optimize the oxide- based memory device.

On Demand available April 26 - June 30, 2021 22 Author Index Bold page numbers indicate presenter — A — Costine, A.: B6-1, 14 Houška, J.: B1-7, 2 Abad, M.: BP-14, 21 Crawford, G.: B4-1, 8 Hovsepian, P.: B8-10, 18 Abadias, G.: BP-8, 20 Czettl, C.: B2-1, 4; B2-9, 5 Hsu, C.: BP-15, 22 Achille, A.: B1-8, 2 Czigány, Z.: B4-2, 8 Hu, L.: B5-4, 12 Affonco, L.: BP-12, 21 — D — Huang, J.: B4-3, 8 Aissani, L.: BP-7, 20; BP-9, 21 Daniel, R.: B4-8, 10; B4-9, 10 Hubicka, Z.: B8-5, 17 Aksakalli, N.: B8-13, 18 De Doncker, R.: B1-13, 2 Humberto Dias da Silva , J.: BP-12, 21 Alhussein, A.: BP-7, 20; BP-9, 21 Debnarova, S.: BP-6, 20 Hwang, S.: B2-8, 4 Ali, S.: B4-14, 11 Delsa, P.: B6-1, 14 — I — Altama, A.: B8-9, 18 Depla , D.: BP-10, 21 Itagaki, N.: B2-8, 4 Alvarado Orozco, J.: B4-7, 9 Depla, D.: B1-13, 2 Ito, T.: B2-6, 4 Alvarado-Orozco, J.: B1-2, 1 Du, H.: BP-13, 21 — J — Alvarez, F.: B4-16, 11 — E — Jäger, N.: B4-9, 10 Anders, A.: B1-15, 3; B7-4, 16 Edwards, T.: B2-14, 6 Jahn, F.: BP-3, 19 Arndt, M.: B6-4, 14 Efeoglu, I.: B8-13, 18 Jiang, Z.: B8-12, 18 Arunachalam , N.: B2-15, 6 Ehiasarian, A.: B8-10, 18 Jimenez, M.: B4-16, 11 — B — Elhadj, S.: B3-1, 7 Jurczyk, B.: B1-9, 2 Bäcke, O.: B2-11, 5 Endrino, J.: B3-4, 7 Jyh-Wei, L.: B3-7, 8 Balachandran, P.: B6-1, 14 Erard, M.: B5-5, 12 — K — Balat-Michelin, M.: B2-12, 5 Espinosa-Arbeláez , D.: B1-2, 1 Kagerer, S.: B5-9, 13 Ballesteros-Arguello, A.: B4-18, 11 Evertz, S.: B4-2, 8 Kamataki, K.: B2-8, 4 Banakh, O.: B5-5, 12 — F — Kaulfuss, F.: B1-5, 1; B3-5, 7 Bartosik, M.: B6-5, 15; B6-7, 15 Faese, F.: B4-4, 9 Keckes, J.: B4-8, 10 Bayu Aji, B.: B3-1, 7 Falabella, S.: B3-1, 7 Kersten, H.: B7-1, 15; B7-3, 16 Beake, B.: B4-5, 9 Fekete, M.: B8-1, 16 Khan, T.: B3-2, 7 Belgroune, A.: BP-9, 21 Feng, J.: B4-5, 9 Kirnbauer, A.: B5-9, 13 Bellido-Gonzalez, V.: B3-4, 7 Fernandez, I.: B8-6, 17 Kiryukhantsev-Korneev, P.: B5-1, 12 Berman, S.: BP-10, 21 Fernández-Martínez, I.: B3-4, 7; B5-7, 13 Kiyokawa, D.: B4-19, 11 Bernatova, K.: B8-1, 16 Fernández-Valdés, D.: B4-18, 11 Klein, P.: B8-1, 16; B8-3, 16; B8-4, 17 Bernátová, K.: BP-1, 19 Fian, A.: B1-14, 3 Klette, M.: B7-1, 15; B7-3, 16 Bih-Show, L.: B3-7, 8 Figueroa, C.: B4-16, 11 Kodambaka, S.: B5-8, 13; B6-4, 14 Bisoffi, F.: B5-5, 12 Fleming, D.: B5-10, 13 Koelker, W.: B2-13, 6 Boman, M.: B2-11, 5 Forslund, A.: B2-11, 5 Koga, K.: B2-8, 4 Boominatha Sellarajan , S.: B2-15, 6 Francelosi Azevedo Neto , N.: BP-12, 21 Kolozsvári, S.: B5-8, 13; B6-4, 14 Böör, K.: B2-11, 5 Frank, F.: B2-1, 4 Konstantiniuk, F.: B2-9, 5 Boron, Ł.: B3-2, 7 Frank, M.: B2-13, 6 Koutná, N.: B6-5, 15; B6-7, 15; B7-4, 16 Bower, A.: B6-2, 14 Franz, R.: B1-15, 3; B7-4, 16 Kozak, T.: B8-5, 17; BP-5, 20 Boyd, R.: BP-13, 21 Friák, M.: B6-5, 15 Krause, J.: B4-2, 8 Brenning, N.: B1-1, 1 Fuji, K.: B4-19, 11 Kretschmer, A.: BP-2, 19 Britun, N.: B8-3, 16 Fukarek, W.: B1-5, 1 Kroker, M.: B8-4, 17 Bublikov, J.: B1-4, 1 — G — Kruelle, T.: B3-5, 7 Büchel, S.: B2-14, 6 Gan, K.: BP-15, 22 Kucheyev, S.: B3-1, 7 Buchinger, J.: B6-7, 15 Gebhardt, B.: B1-5, 1 Kustas, F.: B4-1, 8 Bursikova, V.: BP-6, 20 Gerhards, N.: B1-3, 1 — L — — C — Glechner, T.: B5-8, 13; B6-4, 14 Larsson, H.: B2-11, 5 Cada, M.: B8-5, 17 Goel, S.: B3-4, 7 Lee, .: BP-11, 21 Camacho, N.: B1-2, 1 Golizadeh, M.: B1-15, 3; B7-4, 16 Lee, J.: B3-6, 8 Capek, J.: B8-5, 17 Gómez Ovalle, A.: B4-7, 9 Lei, M.: B8-12, 18 Caro, J.: BP-14, 21 Gómez-Ovalle, A.: B1-2, 1 Lemmer, O.: B2-13, 6 Carvalho, I.: B1-12, 2 González Carmona, J.: B4-7, 9 Leson, A.: B3-5, 7 Carvalho, S.: B1-12, 2 González-Carmona, J.: B1-2, 1 Levashov, E.: B5-1, 12 Castro, J.: B1-12, 2 Grigoriev, S.: B1-4, 1 Li, T.: B6-1, 14 Cavarroc, M.: B1-8, 2 Gruettner, H.: B3-3, 7 Li, Y.: B8-12, 18 Ceballos-Sanchexz, A.: B3-1, 7 Gudmundsson, J.: B1-1, 1 Liao, B.: B5-11, 14 Cedeño-Vente, M.: B1-2, 1 Gumus, B.: B8-13, 18 Li-Chun, C.: B3-7, 8 Cemin, F.: B4-16, 11 — H — Lin, Z.: B4-17, 11 Černý, M.: B6-5, 15 Hahn, R.: B5-8, 13; B6-4, 14; B6-7, 15 Lindahl, E.: B2-11, 5 Chang, Y.: B1-16, 3 Haldan, D.: B3-3, 7 Liskiewicz, T.: B3-2, 7; B4-5, 9 Chang-Liao, K.: B7-5, 16 Halvarsson, M.: B2-11, 5 Liu, K.: B4-17, 11 Charpentier, L.: B2-12, 5 Han, Y.: B3-5, 7 Liu, P.: BP-15, 22 Chason , E.: BP-10, 21 Hans, M.: B4-2, 8; BP-6, 20 Liu, Z.: B2-10, 5 Chason, E.: B6-2, 14; B8-7, 17 Hansen, L.: B7-1, 15 Löfler, L.: B6-5, 15 Chen, D.: B2-12, 5 Hantzenbichler, L.: B6-5, 15 Lorenz, L.: B3-5, 7 Chen, P.: B5-4, 12 Helmersson, U.: BP-13, 21 Lou, B.: BP-11, 21 Chen, S.: B3-6, 8 Henriques, M.: B1-12, 2 Lundin, D.: B1-1, 1; BP-13, 21 Chen, W.: BP-11, 21 Hernández Mendoza, J.: B4-7, 9 Luo, J.: B5-11, 14 Chien, Y.: B7-5, 16 Hlushko, K.: B4-8, 10 — M — Chiu, Y.: BP-15, 22 Hnilica, J.: B8-1, 16; B8-3, 16; B8-4, 17 Maas, M.: B7-3, 16 Chu, F.: B7-5, 16 Hofmann, F.: B3-5, 7 Mackova, A.: B4-8, 10 Chu, J.: B8-9, 18 Holec, D.: B5-8, 13; B6-4, 14; B6-5, 15; B6-7, Maeder, X.: B2-14, 6 Colas, J.: B2-12, 5 15; B7-4, 16 Makowski, S.: B3-5, 7 Colominas, C.: BP-14, 21 Holzapfel, D.: B4-2, 8; BP-6, 20 Marcel Gonçalves Leite , D.: BP-12, 21 Constantin, R.: B5-5, 12 Houlahan, T.: B1-9, 2 Mares, P.: B8-5, 17 Corbella, F.: B4-10, 10 Houska, J.: B5-6, 13; B6-3, 14; BP-5, 20 Matas, M.: B5-6, 13 Author Index 23 Bold page indicates presenter Author Index

Matsushima, H.: B4-19, 11 — R — Terziyska, V.: B1-14, 3 Matthey, J.: B5-5, 12 Raadu, M.: B1-1, 1 Thompson, F.: B4-1, 8 Maus, J.: B3-3, 7 Rajaguru, J.: B2-15, 6 Tkadletz, M.: B1-14, 3; B2-1, 4; B2-9, 5; B4-6, Mayrhofer, P.: B5-8, 13; B5-9, 13; B6-4, 14; Ramachandra Rao, M.: B2-15, 6 9 B6-5, 15; B6-7, 15; BP-2, 19 Ramírez-Reyna, F.: B4-18, 11 Tobola, D.: B3-2, 7 Meindlhumer, M.: B4-9, 10 Ramm, J.: B5-8, 13 Todt, J.: B4-8, 10 Méndez Fernández, Á.: B5-7, 13 Rao, Z.: B8-7, 17; BP-10, 21 Tridon, X.: B4-4, 9 Mendez, A.: B8-6, 17 Řehák, P.: B6-5, 15 Trottenberg, T.: B7-1, 15; B7-3, 16 Meneses-Amador, A.: B4-18, 11 Reinke, P.: B6-1, 14 Tsai, B.: B4-3, 8 Mercier, F.: B2-12, 5; B2-4, 4 Reyes-Carcaño, O.: B4-18, 11 — U — Michau, D.: B1-8, 2 Riedl, H.: B5-8, 13; B6-4, 14 Uglov, V.: BP-8, 20 Michelon, J.: B4-4, 9 Riul, A.: B4-16, 11 — V — Michler, J.: B2-14, 6 Rodríguez-Castro, G.: B4-18, 11 Vasina, P.: B5-3, 12; B8-1, 16; B8-3, 16; BP-6, Miller, J.: B3-1, 7 Rojas, T.: B3-4, 7 20 Minea, T.: B1-1, 1 Ruan, D.: B7-5, 16; BP-15, 22 Vašina, P.: B8-4, 17 Mitterer, C.: B1-15, 3; B4-9, 10 Rudigier, H.: BP-2, 19 Vereschaka, A.: B1-4, 1 Moirangthem, I.: B3-6, 8 Rueß, H.: B4-2, 8 Vignesh, R.: B2-15, 6 Molina-Aldareguia, J.: B3-4, 7; B5-7, 13 — S — Viloan, R.: BP-13, 21 Monclús, M.: B3-4, 7; B5-7, 13 Saito, T.: B4-19, 11 Vlcek, J.: B5-6, 13 Mondragón Rodríguez, G.: B4-7, 9 Sakamoto, Y.: BP-4, 19 Vlček, J.: B1-7, 2 Mondragón-Rodríguez, G.: B1-2, 1 Sala, N.: BP-14, 21 von Fieandt, L.: B2-11, 5 Moritz, Y.: B4-6, 9 Saladukhin, I.: BP-8, 20 — W — Mraz, S.: BP-6, 20 Sánchez-Lopez, J.: B3-4, 7 Wang, H.: B5-11, 14 Music, D.: B4-2, 8 Sánchez-López, J.: BP-14, 21 Wang, W.: B5-11, 14 — N — Sangiovanni, D.: B6-7, 15 Weihnacht, V.: B1-5, 1; B3-5, 7 Nahif, F.: B1-3, 1; B4-9, 10 Santiago Varela, J.: B3-4, 7 Weissmantel, S.: B3-3, 7; BP-3, 19 Nieher, M.: B3-3, 7 Santiago, J.: B5-7, 13; B8-6, 17 Wennberg, A.: B3-4, 7; B5-7, 13; B8-6, 17 Nienhaus, A.: B2-3, 4 Saringer, C.: B1-14, 3; B2-1, 4; B4-6, 9 Wicaksono, S.: B8-9, 18 Nitta, K.: B2-6, 4 Schalk, N.: B1-14, 3; B2-1, 4; B2-9, 5; B4-6, 9 Wisnivesky, D.: B4-16, 11 Nouveau, C.: BP-7, 20 Schaller, F.: B3-5, 7 Woda, M.: B2-13, 6 — O — Schell, N.: B2-1, 4; B4-6, 9 Wojcik, T.: B6-4, 14 Okamoto, N.: B4-19, 11 Schenkel, M.: B1-3, 1 Wu, F.: B4-17, 11 Ondračka, P.: B4-2, 8 Schiffers, C.: B2-13, 6 — X — Ortega Portilla, C.: B4-7, 9 Schlichting, F.: B7-1, 15 Xiang, J.: B4-17, 11 Ou, Y.: B5-11, 14 Schneider, J.: B4-2, 8; BP-6, 20 Xie, T.: B2-14, 6 Ouyang, X.: B5-11, 14 Schorr, D.: B4-12, 10 — Y — — P — Shchelkanov, I.: B1-9, 2 Yalamanchili, K.: BP-2, 19 Pajdarova, A.: B8-5, 17 Shimizu, T.: BP-13, 21 Yang, L.: B3-2, 7 Pan, N.: B8-12, 18 Shiratani, M.: B2-8, 4 Yang, Y.: B4-17, 11 Panizo-Laiz, M.: B3-4, 7; B5-7, 13 Sitnikov, N.: B1-4, 1 Yeh, H.: B7-5, 16 Papa, F.: B8-6, 17 Šlapanská, M.: B8-4, 17 Yi, S.: B7-5, 16 Petho, L.: B2-14, 6 Snyders, R.: B8-3, 16 Yu -Tung, H.: B3-7, 8 Petty, T.: B1-1, 1 Soucek, P.: B5-3, 12; BP-6, 20 Yuan, H.: B8-12, 18 Pohler, M.: B4-6, 9 Spethmann, A.: B7-1, 15 Yuan, M.: B2-16, 6 Polacek, M.: B5-3, 12 Spor, S.: B1-3, 1 — Z — Polcik, P.: B5-9, 13 Stark, A.: B2-1, 4; B4-6, 9 Zabransky, L.: B5-3, 12 Pons, M.: B2-12, 5 Stegemann, C.: BP-12, 21 Zagonel, L.: B4-16, 11 Poulon-Quintin, A.: B1-8, 2 Stubbers, R.: B1-9, 2 Zaid, H.: B5-8, 13 Primetzhofer, D.: B4-2, 8; B5-8, 13 Stupavska, M.: B5-3, 12 Zanáška, M.: BP-13, 21 Prochazka, M.: B5-6, 13 Sugumaran, A.: B8-10, 18 Zawischa, M.: B3-5, 7 Puetz, W.: B2-13, 6 Sze, S.: BP-15, 22 Zhang, X.: B5-11, 14 Purniawan, A.: B8-9, 18 — T — Zimmermann, U.: B1-3, 1 Putz, B.: B2-14, 6 Takuya, M.: BP-4, 19 Zítek, M.: B4-9, 10 — Q — Tan, E.: B8-13, 18 Zlotski, S.: BP-8, 20 Qin, Y.: B4-5, 9 Tanaka, R.: BP-4, 19 Zöhrer, S.: B7-4, 16 Qiu, R.: B2-11, 5 Terashima, K.: B2-6, 4

Author Index 24 Bold page indicates presenter